WO2019048878A1

WO2019048878A1 - A polymerisation process

Info

Publication number: WO2019048878A1
Application number: PCT/GB2018/052551
Authority: WO
Inventors: Michael Kember; James LEELAND; Manuela LANDEL; Robert Smith; Alex MORTON; Samuel DRANE
Original assignee: Econic Technologies Ltd
Priority date: 2017-09-07
Filing date: 2018-09-07
Publication date: 2019-03-14
Also published as: GB201714436D0

Abstract

The present invention relates to a polymerisation process for the reaction of (a) carbon dioxide with an epoxide; and/or (b) an anhydride with an epoxide. The process is carried out in the presence of a chain transfer agent and a catalyst of formula (I): Formula (I) The catalyst comprises groups Y1 and Y2 which are independently a neutral or anionic donor ligand group capable of donating a lone pair to the mental M2. M1 and M2 are independently selected from Zn(ll), Cr(ll), Co(ll), Cu(ll), Mn(ll), Mg(ll), Ni(ll), Fe(ll), Ti(ll), V(ll), Cr(lll), Co(lll), Mn(lll), Ni(lll), Fe(lll), Ca(ll), Ge(ll), Al(lll), Ti(lll), V(lll), Ge(IV), Y(lll), Sc(lll) or Ti(IV). The present invention also relates to a catalyst, and polymers produced by the process using the catalyst and higher polymers such as polyurethanes produced therefrom.

Description

A Polymerisation Process

Field of the Invention

The present invention relates to a polymerisation process, in particular to a polymerisation process for the reaction of carbon dioxide with an epoxide and/or an anhydride with an epoxide in the presence of a bimetallic catalyst and a chain transfer agent, a catalyst and polymers produced by the process using the catalyst.

Background

Environmental and economic concerns associated with depleting oil resources have triggered a growing interest in the chemical conversion of carbon dioxide (C0₂), so as to enable its use as a renewable carbon source. C0₂ is, despite its low reactivity, a highly attractive carbon feedstock, as it is inexpensive, virtually non-toxic, abundantly available in high purity and non- hazardous. Therefore, C0₂ could be a promising substitute for substances such as carbon monoxide, phosgene or other petrochemical feedstocks in many processes. One of the developing applications of C0₂ is copolymerization with epoxides to yield aliphatic polycarbonates. The development of effective catalysts to make such a process profitable is the subject of continuous research. In WO2009/130470 the copolymerisation of an epoxide with C0₂ using a catalyst of a class represented by formula (a) was described:

formula (a)

WO2013/034750 discloses the copolymerisation of an epoxide with C0₂ in the presence of a chain transfer agent using a catalyst of a class represented by formula (b):

formula (b)

Various compounds according to formulae (a) and (b) above were tested for their ability to catalyse the reaction between different epoxides and carbon dioxide. In WO2009/130470 and WO2013/034750 the catalyst systems are fully closed, i.e. the structure around the bimetallic centre forms a 'cage' that fully surrounds said bimetallic centre.

Among the epoxides employed in the copolymerization reactions of the prior art, cyclohexene oxide (CHO) received special interest, as the product, poly(cyclohexene carbonate) (PCHC) shows a high glass transition temperature and reasonable tensile strength.

JP2013163772 discloses the copolymerisation of an epoxide with C0₂ in the presence of a catalyst of a class represented by formula (c) wherein M is Zn and M² a group 6 metal:

Thevenon et a/., 'Dinuclear Zinc Salen Catalysts for the Ring Opening Copolymerization of Epoxides and Carbon Dioxide or Anhydrides', Inorganic Chemistry, 2015, 54, 1 1906-1 1915, discloses the copolymerisation of CHO with C0₂ or anhydrides in the presence of zinc catalysts of formula (d):

formula (d)

Lin et al., 'Bimetallic Nickel Complexes that Bear Diamine-Bis(Benzotriazole Phenolate) Derivatives as Efficient Catalysts for the Copolymerization of Carbon Dioxide with Epoxides', ChemCatCHem, 2016, 8, 984-991 , discloses the copolymensation of CHO and it's derivatives with C0₂ in the presence of catalysts according to formulas (e) and (f):

formula (e)

formula (f) Each of JP2013163772, Thevenon et al and Lin et al exemplify the copolymensation of cyclohexene oxide with C0₂ in the presence of catalysts according to formulae (c), (d) and (e) and (f), respectively. Each of catalysts of formulae (c), (d), (e) and (f) are open at one side of the bimetallic centre, i.e. the structure around the bimetallic centre does not form a 'cage' that fully surrounds said bimetallic centre. None of these documents disclose the use of a chain transfer agent.

It is known that the use of chain transfer agents in the copolymerisation of carbon dioxide with an epoxide and/or an anhydride with an epoxide can poison the catalysts used in said copolymerisation.

The inventors have now surprisingly found that bimetallic catalysts having an open cage structure around a bimetallic centre are active as polymerisation catalysts for the reaction of carbon dioxide with an epoxide and/or an anhydride with an epoxide in the presence of a chain transfer agent. In particular, the inventors have found that a polymerisation process for the reaction of carbon dioxide with an epoxide and/or an anhydride with an epoxide carried out in the presence of a chain transfer agent and a bimetallic catalysts having an open cage structure around a bimetallic centre are better in terms of activity and/or selectivity than the catalysts previously disclosed in the art. Furthermore, if used in conjunction with chain transfer agents they surprisingly do not poison the bimetallic catalysts having an open cage structure around a bimetallic centre.

Summary of the Invention

According to a first aspect of the present invention there is provided a polymerisation process for the reaction of:

(a) carbon dioxide with an epoxide; and/or

(b) an anhydride with an epoxide,

wherein the process is carried out in the presence of a chain transfer agent and a catalyst of formula (I):

formula (I) wherein R and R² are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine group, -NCR ³R¹⁴, an amine, an ether -OR¹⁵, -R ⁶OR¹⁷, an ester group - OC(0)R¹⁰ or -C(0)OR¹⁰, an amido group -NR⁹C(0)R⁹ or -C(0)-NR⁹(R⁹), -COOH, -C(0)R¹⁵, -OP(0)(OR ⁸)(OR¹⁹) ,-P(O)R²⁰R²¹ , -P(0)(OR)(OR), -OP(0)R(OR), a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;

R³ is independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene, may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic; R⁴ is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;

R⁹, R ⁰, R ³, R ⁴, R ⁸, R ⁹, R²⁰ and R² are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group;

E is C, E² is O, S or NH or E is N and E² is O;

E³ is N, NR⁵, O or S, wherein when E³ is N, is , and when E³ is NR⁵, O or S, is ;

R⁵ is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkylC(0)OR¹⁰, -alkylnitrile, or alkylaryl; X, when present, is independently selected from OC(0)R^x, OS0₂R^x, OSOR^x, OSO(R^x)₂, S(0)R^x, OR^x, phosphinate, halide, nitrate, hydroxyl, carbonate, amino, nitro, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl; m and n are independently integers selected from the range 0-3, such that the sum of m and n is 0-5;

R^x is independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group;

each G is independently absent or a neutral or anionic donor ligand which is a Lewis base; Y and Y² are independently a neutral or anionic donor group capable of donating a lone pair to the metal M²;

M and M² are independently selected from Zn(ll), Cr(ll), Co(ll), Cu(ll), Mn(ll), Mg(ll), Ni(ll), Fe(ll), Ti(ll), V(ll), Cr(lll), Co(lll), Mn(lll), Ni(lll), Fe(lll), Ca(ll), Ge(ll), Al(lll), Ti(lll), V(lll), Ge(IV), Y(lll), Sc(lll) or Ti(IV).

According to a second aspect of the present invention there is provided a catalyst of formula (II):

formula (II) wherein R and R² are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine group, -NCR ³R¹⁴, an amine, an ether -OR¹⁵, -R ⁶OR¹⁷, an ester group - OC(0)R¹⁰ or -C(0)OR¹⁰, an amido group -NR⁹C(0)R⁹ or -C(0)-NR⁹(R⁹), -COOH, -C(0)R¹⁵, -OP(0)(OR ⁸)(OR¹⁹) ,-P(O)R²⁰R²¹, -P(0)(OR)(OR), -OP(0)R(OR), a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;

E is C, E² is O, S or NH or E is N and E² is O;

R⁵ is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkylC(0)OR¹⁰, -alkylnitrile, or alkylaryl;

X, when present, is independently selected from OC(0)R^x, OS0₂R^x, OSOR^x, OSO(R^x)₂, S(0)R^x, OR^x, phosphinate, halide, nitrate, hydroxyl, carbonate, amino, nitro, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl; m and n are independently integers selected from the range 0-3, such that the sum of m and n is 0-5;

each G is independently absent or a neutral or anionic donor ligand which is a Lewis base; Y and Y² are independently a neutral or anionic donor group capable of donating a lone pair to the metal M² selected from a group with the lone pair donated by a non-aromatic nitrogen atom, a group with the lone pair donated by a carbene carbon atom, a group with the lone pair donated by a carbonyl oxygen atom and a group with the lone pair donated by a carboxylate oxygen atom;

According to a third aspect of the present invention there is provided a polymerisation process for the reaction of :

(a) carbon dioxide with an epoxide; and/or (b) an anhydride with an epoxide,

wherein the process is carried out in the presence of a chain transfer agent and a catalyst according to the second aspect of the present invention. According to a fourth aspect of the present invention there is provided a polymer produced by the process of the first or third aspects of the present invention.

Definitions

For the purpose of the present invention, an aliphatic group is a hydrocarbon moiety that may be straight chain or branched and may be completely saturated, or contain one or more units of unsaturation, but which is not aromatic. The term "unsaturated" means a moiety that has one or more double and/or triple bonds. The term "aliphatic" is therefore intended to encompass alkyl, alkenyl or alkynyl groups including multivalent equivalents such as alkylene, alkenylene and alkynylene, and combinations thereof. An aliphatic group is preferably a C_1-2o aliphatic group, that is, an aliphatic group with 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, an aliphatic group is a CMS aliphatic, more preferably a C_{1 -12} aliphatic, more preferably a C_{1 -10} aliphatic, even more preferably a C_{1 -8} aliphatic, such as a C_{1 -6} aliphatic group. An alkyl group is preferably a "C_1-2o alkyl group", that is an alkyl group that is a straight or branched chain with 1 to 20 carbons. The alkyl group therefore has 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, an alkyl group is a CMS alkyl, preferably a C_{1 -12} alkyl, more preferably a C_{1 -10} alkyl, even more preferably a C_{1 -8} alkyl, even more preferably a C_{1 -6} alkyl group. Specifically, examples of "C_{1 -20} alkyl group" include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 1 ,1 -dimethylpropyl group, 1 ,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1 -ethylpropyl group, n-hexyl group, 1 -ethyl-2-methylpropyl group, 1 ,1 ,2-trimethylpropyl group, 1 -ethylbutyl group, 1 -methylbutyl group, 2-methylbutyl group, 1 ,1 -dimethylbutyl group, 1 ,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1 ,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 3-methylpentyl group and the like. Alkenyl and alkynyl groups are preferably "C₂.₂₀ alkenyl" and "C₂.₂₀ alkynyl", more preferably "C_2-15 alkenyl" and "C_2-15 alkynyl", even more preferably "C_2-12 alkenyl" and "C_2-12 alkynyl", even more preferably "C_2-10 alkenyl" and "C_2-10 alkynyl", even more preferably "C₂.₈ alkenyl" and "C₂.₈ alkynyl", most preferably "C₂.₆ alkenyl" and "C₂.₆ alkynyl" groups, respectively. Alkylene is divalent but otherwise defined as an Alkyl group above. Likewise, alkenylene and alkynylene are defined as divalent equivalents of alkenyl and alkynyl above.

A heteroaliphatic group (including heteroalkyi, heteroalkenyl and heteroalkynyl) is an aliphatic group as described above, wherein one or more carbon atoms are replaced by heteroatoms. Heteroaliphatic groups therefore preferably contain from 2 to 21 atoms, preferably from 2 to 16 atoms, more preferably from 2 to 13 atoms, more preferably from 2 to 1 1 atoms, more preferably from 2 to 9 atoms, even more preferably from 2 to 7 atoms, wherein at least one atom is a carbon atom and at least one atom is a heteroatom. Particularly preferred heteroatoms are selected from O, S, N, P and Si. When heteroaliphatic groups have two or more heteroatoms, the heteroatoms may be the same or different.

Heteroalkylene is divalent but otherwise defined as an heteroalkyi group above. Likewise, heteroalkenylene and heteroalkynylene are defined as divalent equivalents of heteroalkenyl and heteroalkynyl above. An alicyclic group is a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic (including fused, bridging and spiro-fused) ring system which has from 3 to 20 carbon atoms, that is an alicyclic group with 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, an alicyclic group has from 3 to 15, more preferably from 3 to 12, even more preferably from 3 to 10, even more preferably from 3 to 8 carbon atoms, even more preferably from 3 to 6 carbons atoms. The term "alicyclic" encompasses cycloalkyl, cycloalkenyl and cycloalkynyl groups. It will be appreciated that the alicyclic group may comprise an alicyclic ring bearing one or more linking or non-linking alkyl substituents, such as -CH₂-cyclohexyl. Specifically, examples of the C₃_₂o cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl and cyclooctyl.

A heteroalicyclic group is an alicyclic group as defined above which has, in addition to carbon atoms, one or more ring heteroatoms, which are preferably selected from O, S, N, P and Si. Heteroalicyclic groups preferably contain from one to four heteroatoms, which may be the same or different. Heteroalicyclic groups preferably contain from 5 to 20 atoms, more preferably from 5 to 14 atoms, even more preferably from 5 to 12 atoms.

An aryl group is a monocyclic or polycyclic ring system having from 5 to 20 carbon atoms. An aryl group is preferably a "C₆. ₂ aryl group" and is an aryl group constituted by 6, 7, 8, 9, 10, 1 1 or 12 carbon atoms and includes condensed ring groups such as monocyclic ring group, or bicyclic ring group and the like. Specifically, examples of "C₆. ₀ aryl group" include phenyl group, biphenyl group, indenyl group, naphthyl group or azulenyl group and the like. It should be noted that condensed rings such as indan and tetrahydro naphthalene are also included in the aryl group. A heteroaryl group is an aryl group having, in addition to carbon atoms, from one to four ring heteroatoms which are preferably selected from O, S, N, P and Si. A heteroaryl group preferably has from 5 to 20, more preferably from 5 to 14 ring atoms. Specifically, examples of a heteroaryl group include pyridine, imidazole, methylimidazole and dimethylaminopyridine.

Examples of alicyclic, heteroalicyclic, aryl and heteroaryl groups include but are not limited to cyclohexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole, carbazole, cinnoline, dioxin, dioxane, dioxolane, dithiane, dithiazine, dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isoxazole, isothiazole, morpholine, napthyridine, oxazole, oxadiazole, oxathiazole, oxathiazolidine, oxazine, oxadiazine, phenazine, phenothiazine, phenoxazine, phthalazine, piperazine, piperidine, pteridine, purine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, quinoline, quinoxaline, quinazoline, quinolizine, tetrahydrofuran, tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole, thiazine, thiazole, thiomorpholine, thianaphthalene, thiopyran, triazine, triazole, and trithiane.

Arylene is divalent but otherwise defined as an aryl group above. Likewise heteroarylene is defined as divalent equivalents of heteroaryl and cycloalkylene as divalent equivalents of alicyclic and heteroalicyclic above.

The term "halide" or "halogen" are used interchangeably and, as used herein mean a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, preferably a fluorine atom, a bromine atom or a chlorine atom, and more preferably a fluorine atom.

A haloalkyl group is preferably a "C_1-2o haloalkyl group", more preferably a "CMS haloalkyl group", more preferably a "C_{1 -12} haloalkyl group", more preferably a "C_{1 -10} haloalkyl group", even more preferably a "C_{1 -8} haloalkyl group", even more preferably a "C_{1 -6} haloalkyl group" and is a C_1-2o alkyl, a CMS alkyl, a C_{1 -12} alkyl, a C_{1 -10} alkyl, a C_{1 -8} alkyl, or a C_{1 -6} alkyl group, respectively, as described above substituted with at least one halogen atom, preferably 1 , 2 or 3 halogen atom(s). Specifically, examples of "C_{1 -20} haloalkyl group" include fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluroethyl group, trifluoroethyl group, chloromethyl group, bromomethyl group, iodomethyl group and the like. An alkoxy group is preferably a "C_{1 -20} alkoxy group", more preferably a "CMS alkoxy group", more preferably a "C_{1 -12} alkoxy group", more preferably a "C_{1 -10} alkoxy group", even more preferably a "C_{1 -8} alkoxy group", even more preferably a "C_{1 -6} alkoxy group" and is an oxy group that is bonded to the previously defined C_{1 -20} alkyl, CMS alkyl, C_{1 -12} alkyl, C_{1 -10} alkyl, C_{1 -8} alkyl, or C_{1 -6} alkyl group respectively. Specifically, examples of "C_{1 -20} alkoxy group" include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, iso-pentyloxy group, sec- pentyloxy group, n-hexyloxy group, iso-hexyloxy group, , n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-eicosyloxy group, 1 ,1 -dimethylpropoxy group, 1 ,2-dimethylpropoxy group, 2,2-dimethylpropoxy group, 2- methylbutoxy group, 1 -ethyl-2-methylpropoxy group, 1 ,1 ,2-trimethylpropoxy group, 1 ,1 - dimethylbutoxy group, 1 ,2-dimethylbutoxy group, 2,2-dimethylbutoxy group, 2,3- dimethylbutoxy group, 1 ,3-dimethylbutoxy group, 2-ethylbutoxy group, 2-methylpentyloxy group, 3-methylpentyloxy group and the like.

An aryloxy group is preferably a "C₅_₂o aryloxy group", more preferably a "C₆. ₂ aryloxy group", even more preferably a "C₆. ₀ aryloxy group" and is an oxy group that is bonded to the previously defined C₅_₂o aryl, C₆. ₂ aryl, or C₆. ₀ aryl group respectively.

An alkylthio group is preferably a "C_{1 -2}o alkylthio group", more preferably a "CMS alkylthio group", more preferably a "C_{1 -12} alkylthio group", more preferably a "C_{1 -10} alkylthio group", even more preferably a "C_{1 -8} alkylthio group", even more preferably a "C_{1 -6} alkylthio group" and is a thio (-S-) group that is bonded to the previously defined C_{1 -2}o alkyl, CMS alkyl, C_{1 -12} alkyl, C_{1 -10} alkyl, C_{1 -8} alkyl, or C_{1 -6} alkyl group respectively. An alkylthio group utilised as a substituent as defined herein, may be connected via either a carbon atom of the alkyl group as defined above or the sulphur atom of the thio group. An arylthio group is preferably a "C₅.₂₀ arylthio group", more preferably a "C₆. ₂ arylthio group", even more preferably a "C₆. ₀ arylthio group" and is an thio (-S-) group that is bonded to the previously defined C₅.₂₀ aryl, C₆. ₂ aryl, or C₆-io aryl group respectively.

An alkylaryl group is preferably a "C₆. ₂ aryl C_{1 -20} alkyl group", more preferably a preferably a "C₆-i₂ aryl C_{1 -16} alkyl group", even more preferably a "C₆. ₂ aryl C_{1 -6} alkyl group" and is an aryl group as defined above bonded at any position to an alkyl group as defined above. The point of attachment of the alkylaryl group to a molecule may be via the alkyl portion and thus, preferably, the alkylaryl group is -CH₂-Ph or -CH₂CH₂-Ph. An alkylaryl group can also be referred to as "aralkyl". A silyl ether group is preferably a group OSi(R⁷)₃ wherein each R⁷ can be independently an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, each R⁷ can be independently an unsubstituted aliphatic, alicyclic or aryl. Preferably, each R⁷ is an optionally substituted phenyl or optionally substituted alkyl group selected from methyl, ethyl, propyl or butyl (such as n-butyl or tert-butyl (tBu)). Exemplary silyl ether groups include OSi(CH₃)₃, OSi(C₂H₅)₃, OSi(C₆H₅)₃, OSi(CH₃)₂C(CH₃)₃, OSi(tBu)₃ and OSi(C₆H₅)₂C(CH₃)₃.

A nitrile group (also referred to as a cyano group) is a group CN.

An imine group is a group -CR⁸NR⁸, preferably a group -CHNR⁸ wherein R⁸ is an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R⁸ is unsubstituted aliphatic, alicyclic or aryl. Preferably R⁸ is an alkyl group selected from methyl, ethyl or propyl.

An amido group is preferably-NR⁹C(0)R⁹ or -C(0)-NR⁹(R⁹) wherein R⁹ can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R⁹ is unsubstituted aliphatic, alicyclic or aryl. Preferably R⁹ is hydrogen, methyl, ethyl, propyl or phenyl. The amido group may be terminated by hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group.

An ester group is preferably -OC(0)R¹⁰ or -C(0)OR¹⁰ wherein R ⁰ can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R ⁰ is unsubstituted aliphatic, alicyclic or aryl. Preferably R ⁰ is hydrogen, methyl, ethyl, propyl or phenyl. The ester group may be terminated by hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group.

An acetylide group contains a triple bond -C≡C-R¹¹ , preferably wherein R can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. For the purposes of the invention when R is alkyl, the triple bond can be present at any position along the alkyl chain. In certain embodiments, R is unsubstituted aliphatic, alicyclic or aryl. Preferably R is methyl, ethyl, propyl or phenyl.

An amino group is preferably -NH₂, -NHR ² or -N(R ²)₂ wherein R ² can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, a silyl group, aryl or heteroaryl group as defined above. It will be appreciated that when the amino group is N(R ²)₂, each R ² group can be the same or different. In certain embodiments, each R ⁹ is independently an unsubstituted aliphatic, alicyclic, silyl or aryl. Preferably R ² is methyl, ethyl, propyl, butyl, Si(CH₃)₃ or phenyl.

An ether group is preferably -OR¹⁵ or -R ⁶OR¹⁷ wherein R ⁵, R ⁶ and R ⁷ can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R ⁵, R ⁶ and R ⁷ are each unsubstituted aliphatic, alicyclic or aryl. Preferably, R ⁵, R ⁶ and R ⁷ are each methyl, ethyl, propyl or phenyl. The ether group may be terminated by hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group. Groups R ³, R ⁴, R ⁸, R ⁹, R²⁰ and R² can be a hydrogen an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R ³, R ⁴, R ⁸, R ⁹, R²⁰ and R² are each unsubstituted aliphatic, alicyclic or aryl. Preferably, R ³, R ⁴, R ⁸, R ⁹, R²⁰ and R² are each hydrogen, methyl, ethyl, propyl or phenyl.

A sulfoxide is preferably -S(0)R²² and a sulfonyl group is preferably -S(0)₂R²² wherein R²² can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R²² is unsubstituted aliphatic, alicyclic or aryl. Preferably R²² is hydrogen, methyl, ethyl, propyl or phenyl.

A sulfinate group is preferably -OSOR²³ wherein R²³ can be hydrogen, an aliphatic, heteroaliphatic, haloaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R²³ is unsubstituted aliphatic, alicyclic or aryl. Preferably R²³ is hydrogen, methyl, ethyl, propyl or phenyl.

By the term "phosphonium" as used herein is meant the cation comprising the formula P(R²⁴)₄ ⁺, typically PH₄ ⁺ wherein R²⁴ can be a hydrogen an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments R²⁴ is unsubstituted aliphatic, alicyclic or aryl. Preferably, R²⁴ is hydrogen, methyl, ethyl, propyl or phenyl.

A silyl group is preferably a group -Si(R²⁵)₃, wherein each R²⁵ can be independently an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, each R²⁵ is independently an unsubstituted aliphatic, alicyclic or aryl. Preferably, each R²⁵ is an alkyl group selected from methyl, ethyl or propyl.

Any of the aliphatic (including alkyl, alkenyl, alkynyl, alkylene, alkenylene and alkynylene), heteroaliphatic, (including heteroalkyl, heteroalkenyl, heteroalkynyl, heteroalkylene, heteroalkenylene and heteroalkynylene), alicyclic, cycloalkylene, heteroalicyclic, aryl, arylene, heteroaryl, heteroarylene haloalkyl, alkoxy, aryloxy, alkylthio, arylthio, alkylaryl, silyl, silyl ether, ester, sulfoxide, sulfonyl, imine, acetylide, amino, sulfonate or amidogroups wherever mentioned above, particularly when mentioned as optionally substituted above may be optionally substituted by halogen, hydroxy, nitro, alkoxy, aryloxy, alkylthio, arylthio, heteroaryloxy, alkylaryl, amino, amido, imine, nitrile, silyl, silyl ether, ester, sulfoxide, sulfonyl, acetylide, sulfonate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl groups (for example, optionally substituted by halogen, hydroxy, nitro, alkoxy, aryloxy, alkylthio, arylthio, amino, imine, nitrile, silyl, sulfoxide, sulfonyl, sulfonate or acetylide). When we use the term "optionally substituted" at the start of a list of chemical species we mean that all of the species in the list which can be substituted may be optionally substituted; that is we do not mean that only the first species mentioned in the list may be optionally substituted. The term optionally substituted when used herein means unsubstituted or substituted with a suitable group. Suitable groups will be known to the skilled person. Generally, such groups would not significantly detrimentally affect the function of the substituted group or of a larger moiety to which the substituted group is attached. In some cases, the skilled person would expect the substituent to improve the function of the substituted group.

Detailed Description

Catalyst

The polymerisation process according to the first aspect of the present invention is carried out in the presence of a catalyst of formula (I).

Each of the occurrences of the groups R and R² may be the same or different. Preferably, R and R² are independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, heteroalicyclic, alkoxy, aryloxy or alkylthio. Preferably, each occurrence of R² is the same, and is hydrogen.

Even more preferably, R² is hydrogen and R is independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and optionally substituted alkyl, alkenyl, aryl, heteroaryl, heteroalicyclic, alkoxy, aryloxy, alkylthio, arylthio, such as hydrogen, C^alkyl (e.g. haloalkyl), alkoxy, aryl, halide, nitro, sulfonyl, silyl and alkylthio, for example, ,t- butyl, n-butyl, i-propyl, methyl, piperidinyl, methoxy, hexyl methyl ether, -SCH₃, -S(C₆H₅), H, nitro, trimethylsilyl, methylsulfonyl (-S0₂CH₃), triethylsilyl, halogen or phenyl.

Each occurrence of R can be the same or different, and R and R² can be the same or different. Preferably, each occurrence of R is the same. Preferably, each occurrence of R² is the same. When R and R² are the same, preferably each occurrence of R and R² is methyl. Preferably, each occurrence of R is the same, and each occurrence of R² is the same, and R is different to R². Preferably, both occurrences of R are the same, and are selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, heteroalicyclic, alkoxy, aryloxy, or alkylthio. More preferably, both occurrences of R are the same, and are selected from halide, sulfoxide, silyl, and an optionally substituted alkyl, heteroaryl or alkoxy. Still more preferably, both occurrences of R are the same, and are selected from H, alkyl, aryl, alkoxy, trialkylsilyl such as triethylsilyl, or halide. More preferably still, both occurrences of R are the same, and are selected from H, alkyl, phenyl, halide or trialkylsilyl. Most preferably, both occurrences of R are the same, and are selected from H, methyl, ethyl, n-propyl, i-propyl n-butyl, t-butyl, t-amyl or t-octyl.

It will be appreciated that the group R³ can be the divalent alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene or heteroalkynylene group which may optionally be interrupted by an aryl, heteroaryl, alicyclic or heteroalicyclic group, or may be a divalent arylene or cycloalkylene group which acts as a bridging group between two nitrogen centres in the compound of formula (I), (la) and (II). Thus, where R³ is an alkylene group, such as 2,2- dimethylpropane-1 ,3-diyl, the R³ group has the structure -CH2-C(CH₃)2-CH2-. The definitions of the alkyl, aryl, cycloalkyi etc groups set out herein therefore also relate respectively to the divalent alkylene, arylene, cycloalkylene etc groups set out for R³, and may also be optionally substituted. Exemplary options for R³ include ethane-1 ,2-diyl, 2, 2-fluoropropane-1 ,3-diyl, 2,2- dimethylpropane-1 ,3-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, phenylene, cyclohexane-1 ,2-diyl, cyclohexane-1 ,4-diyl or biphenylene. When R³ is cyclohexane-1 ,2-diyl or cyclohexane-1 ,4- diyl, it can be the racemic, RR- or SS- forms.

R³ can be independently selected from substituted or unsubstituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene or heteroalkynylene, arylene or cycloalkylene. Preferably, R³ is selected from substituted or unsubstituted alkylene, cycloalkylene, alkenylene, heteroalkylene and arylene. More preferably, R³ is selected from - CH2C(CH3)2CH2-, -CH2CH2CH2-, -CH2CH(CH3)CH2-, -CH2C(CH2C6H5)2CH2-, ^— (C6H4)-, CH2CH2-, -CH2-CH2CH2CH2-, -CH₂CH2N(CH3)CH₂CH2-, -(C₆H₁₀)- or -CH2CH₂CH(C₂H5)-. Still more preferably R³ is selected from -CH₂C(CH₃)2CH2-, -CH₂CH₂-, -CH₂CH₂CH₂-, - CH₂CH(CH₃)CH₂-, -CH₂C(CH₂C₆H5)2CH2-, -CH2CH₂CH(C₂H5)-, -CH2CH2CH2CH2-. More preferably still, R³ is selected from -CH₂C(CH₃)2CH2-, CH₂CH₂CH₂-, -CH₂CH(CH₃)CH₂- and -

R³ can be independently selected from substituted or unsubstituted alkylenes and substituted or unsubstituted arylenes, preferably substituted or unsubstituted propylenes, such as propane-1 ,3-diyl and 2, 2-dimethylpropane-1 ,3-diyl, and substituted or unsubstituted phenylene or biphenylene. Preferably both occurrences of R³ are the same. Even more preferably R³ is a substituted propane-1 ,3-diyl, such as 2, 2-di(alkyl)propane-1 ,3-diyl, especially 2,2- dimethylpropane-1 ,3-diyl.

Preferably, each R⁴ is independently selected from hydrogen, and optionally substituted aliphatic or aryl. More preferably, each R⁴ is independently selected from hydrogen or optionally substituted alkyl or aryl. Even more preferably, each R⁴ is the same, and is selected from hydrogen or optionally substituted alkyl or aryl. Exemplary R⁴ groups include hydrogen, methyl, ethyl, n-propyl, n-butyl, phenyl and trifluoromethyl, preferably hydrogen, methyl or trifluoromethyl. Even more preferably, each R⁴ is hydrogen. In preferred combinations of the R⁴ group and R group, R is selected from H, methyl, ethyl, n- propyl, n-butyl, t-butyl, t-octyl, CI, Br, F, nitro, trimethylsilyl, triethylsilyl, methylthio and methoxy and R⁴ is selected from H, methyl, ethyl, n-propyl, phenyl and trifluoromethyl.

Each occurrence of E may be the same or different. Preferably, each occurrence of E is the same. Each occurrence of E² may be the same or different. Preferably, each occurrence of E² is the same. Preferably, E is C and E² is O, S or NH more preferably E is C and E² is O.

Each occurrence of E³ may be the same or different. Preferably, each occurrence of E³ is the same. Preferably R⁵, when present, is independently selected from hydrogen or optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroalkenyl, heteroalkynyl, heteroaryl, - alkylC(0)R¹⁰ or -alkylnitrile. Each R⁵, when present, may be the same or different. Preferably, R⁵, when present, is selected from hydrogen or optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl or heteroaryl. More preferably, each R⁵, when present, is the same and is selected from hydrogen or optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl or heteroaryl. Exemplary R⁵ groups include H, Me, Et, Bn, iPr, tBu or Ph. Even more preferably, each R⁵, when present, is hydrogen or alkyl. Most preferably, each R⁵, when present, is hydrogen.

Y and Y² are groups which are capable of donating a lone pair of electrons to the metal M². The atom of the Y and Y² groups which donate the lone pair of elections typically forms a bond between Y and Y², respectively, and the metal, M². Y and Y² may be the same or different. Preferably, Y and Y² are the same. The atom of the Y and/or Y² group that donates the lone pair is typically a hetero atom selected from oxygen, nitrogen or sulphur or a carbene carbon.

Accordingly, Y and Y² may be hetero or a group containing a heteroatom capable of donating a lone pair. Typically the lone pair is provided by a nitrogen, sulphur or oxygen atom, more typically by a nitrogen or oxygen atom, most typically by a nitrogen atom. Y and Y² may independently comprise from 1 to 20 atoms, preferably from 1 to 15 atoms, more preferably from 1 to 10 atoms.

Preferably, Y and Y² may be independently selected from O, S, -^~NC(0)R¹⁰, -C(0)N^"R¹⁰, - C(0)0^", -C(0)OR¹⁰, -C(0)R¹⁰ , -C(R ⁰)₂C(O)N^"(R¹⁰), optionally substituted heteroaliphatic such as -OR¹⁰, -SR ⁰, - NR¹⁰, -N(R ⁰)₂, -C(R ⁰)₂N(R ⁰)₂, -C(R ⁰)=N(R¹⁰), or optionally substituted heteroalicyclic or heteroaryl or an optionally substituted carbene structure, wherein R ⁰ is independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group. More preferably, Y and Y² may be independently selected from O^", S^", -OR¹⁰, -SR¹⁰, -^~N(R¹⁰), -N(R ⁰)₂, -C(R ⁰)₂N(R ⁰)₂, -C(R ⁰)=N(R¹⁰), -^~NC(0)R¹⁰, -C(0)0, - C(0)OR¹⁰, C(0)R¹⁰ or optionally, imidazoline, 'abnormal' imidazoline (wherein the 'abnormal' imidazoline has a positive and a negative charge on the heterocycle due to the position of the double bond), imidazolidine, pyrrolidine, pyrroline, triazoline, thiazoline oxazole, oxazoline, imidazoylidene, imidazolinylidene, thiazolylidene, oxazolylidene, triazolylidene, benzimidazolylidene, pyrrolidinylidene or 'abnormal imidazolylidene or N,N'-diamidocarbene, optionally substituted pyridine, imidazole, methyl imidazole, benzimidazole, pyrrole, triazole, thiazole, benzimidazoline, benzotriazole, wherein R ⁰ is independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group. When Y and Y² are independently selected from optionally substituted heteroaliphatic, heteroalicyclic or heteroaryl, the optionally substituted heteroaliphatic heteroalicyclic or heteroaryl contains a hetero atom that is capable of donating the lone pair to metal M². When Y and Y² are independently selected from an optionally substituted carbene structure which may or may not be heteroaliphatic, heteroalicyclic or heteroaryl, the optionally substituted carbene structure contains a carbon atom that is capable of donating the lone pair to metal M².

Still more preferably, Y and Y² may be independently selected from O, -OR¹⁰, -N(R ⁰)₂ . C(R ⁰)₂N(R ⁰)₂, -C(R ⁰)₌N(R¹⁰)_, -C(0)0^", -C(0)R¹⁰, optionally substituted imidazolylidene, benzimidazolylidene, imidazolinylidene, or pyrrole.

Most preferably, Y and Y² are independently selected from O, -OCH₃ -C(=0)H, -CH₂N(CH₃)₂, -CH₂N(H)(CH₂CH(CH₃)₂), -CH=N(CH₂CH(CH₃)₂), -CH₂-piperidine or benzotriazine.

The lone pair donating atom of the Y and Y² groups may independently be attached directly to the remainder of the catalyst of formula (I), via a bond to the respective aryl group, or may be attached to the remainder of the catalyst of formula (I) via a linking group attached to the respective aryl group. Preferably, the linking group, when present in Y and/or Y², is selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene. More preferably, the linking group, when present in Y and/or Y², is selected from optionally substituted alkylene, alkenylene, alkynylene or arylene, even more preferably optionally substituted alkylene of arylene. Preferably, the linking group, when present in Y and/or Y², is optionally substituted C^-C_w alkylene, more preferably optionally substituted C^-C₆ alkylene, even more preferably optionally substituted C^-C₄ alkylene, most preferably methylene. For the avoidance of doubt, when the lone pair donating atom of the in Y and/or Y² groups is a carbene carbon, the carbene carbon is not attached directly to the remainder of the catalyst of formula (I).

The heteroatom of the Y and Y² groups may be attached to the respective aryl group of the remainder of the catalyst of formula (I) via the linking group, when present, by any suitable number of atoms, preferably 1 to 10 atoms, more preferably 1 to 6 atoms, even more preferably 1 to 4 atoms, most preferably 1 to 2 atoms. It will be appreciated that when the heteroatom of the Y and/or Y² groups is attached directly to the respective aryl group of the remainder of the catalyst of formula (I), no linking group is present.

It will be appreciated that X may act as the initiating species for the process of the present invention. Each X is independently selected from OC(0)R^x, OS0₂R^x, OSO(R^x)₂, OR^x, halide, nitrate, hydroxyl, carbonate, amido or optionally substituted aliphatic, heteroaliphatic (for example silyl), alicyclic, heteroalicyclic, aryl or heteroaryl. R_x is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl. Preferably, X is OC(0)R^x or OR^x. Preferably, R^x is independently hydrogen, optionally substituted aliphatic, haloaliphatic, aryl, heteroaryl, silyl, or alkylaryl. Exemplary options for X include OCOCH₃, OCOCF₃, OSO2C7H7, OSO(CH₃)₂, Et, Me, PhOEt, OMe, OiPr, OtBu, CI, Br, I, F, N(iPr)₂ or N(SiMe₃)₂.

When G is not absent, it is a group which is capable of donating a lone pair of electrons (i.e. a Lewis base). Each G may be neutral or negatively charged. If G is negatively charged, then one or more positive counterions will be required to balance out the change of the complex. Suitable positive counterions include group 1 metal ions (Na⁺, K⁺, etc), group 2 metal ions (Mg²⁺, Ca²⁺, etc), ammonium ions (i.e. N(R²⁶)₄ ⁺), iminium ions (i.e. (R ²)₂C=N(R²⁶)₂ ⁺, such as bis(triphenylphosphine)iminium ions) or phosphonium ions (P(R²⁶)₄ ⁺), wherein each R²⁶ is independently selected from hydrogen or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl. Preferably, G is independently selected from an optionally substituted heteroaliphatic group, an optionally substituted heteroalicyclic group, an optionally substituted heteroaryl group, a halide, hydroxide, hydride, a carboxylate and water. More preferably, G is independently selected from water, an alcohol, a substituted or unsubstituted heteroaryl (imidazole, methyl imidazole, pyridine, 4-dimethylaminopyridine, pyrrole, pyrazole, etc), an ether dimethyl ether, diethylether, cyclic ethers, etc), a thioether, carbene, a phosphine, a phosphine oxide, a substituted or unsubstituted heteroalicyclic (morpholine, piperidine, tetrahydrofuran, tetrahydrothiophene, etc), an amine, an alkyl amine trimethylamine, triethylamine, etc), acetonitrile, an ester (ethyl acetate, etc), an acetamide (dimethylacetamide, etc), a sulfoxide (dimethylsulfoxide, etc), a carboxylate, a hydroxide, hydride, a halide, a nitrate, a sulfonate, etc. In some embodiments, one or both instances of G is independently selected from optionally substituted heteroaryl, optionally substituted heteroaliphatic, optionally substituted heteroalicyclic, halide, hydroxide, hydride, an ether, a thioether, carbene, a phosphine, a phosphine oxide, an amine, an alkyl amine, acetonitrile, an ester, an acetamide, a sulfoxide, a carboxylate, a nitrate or a sulfonate. In some embodiments, one or both instances of G is negatively charged (for example, halide). In further embodiments, one or both instances of G is an optionally substituted heteroaryl.

It will be appreciated that although in formula (I) and formula (II) below, the groups X and G are illustrated as being associated with a single Iv^ or M₂ metal centre, one or more X and G groups may form a bridge between the Iv^ and M₂ metal centres. For example, an X group may be associated with a single M metal centre as shown in formula (I) and formula (II) below, or a X group may be associated with both metal centres and form a bridge between the two metal centres, as shown below in formula (la):

formula (la)

Preferably, for the formulas I, la and II herein M and M² are independently selected from Zn(ll), Cr(lll), Co(ll), Mn(ll), Mg(ll), Fe(ll) or Fe(lll), most preferably from Zn(ll), Co(ll) or Mg(ll).

Preferably, at least one of M or M² may be selected from Ni(ll), Ni(lll), Co(ll), Co(lll), Cr(ll), Cr(lll), Fe(ll), Fe(lll), Mn(lll), Al(lll), Zn(ll) or Mg(ll). In certain embodiments, each occurrence of M and M² may be different. Preferably, each occurrence of M and M² is different and M or M² is Ni(ll) or Ni(lll) and the other of M or M² is Fe(ll), Fe(lll), Cr(lll), Al(lll), Mg(ll), Zn(ll), Co(ll) or Co(lll), more preferably M or M² is Ni(ll) and the other of M or M² is Mg(ll), Zn(ll), Co(ll), Co(lll) or Cr(lll). Preferably, each occurrence of M and M² is different and M or M² is Zn(ll) and the other of M or M² is Mg(ll).

In certain embodiments, each occurrence of M and M² is the same. Preferably, each occurrence of M and M² may be the same and may be Ni(ll), Ni(lll), Fe(ll), Fe(lll), Mn(lll), Cr(ll), Cr(lll), Co(ll), Co(lll), Zn(ll) or Mg(ll), more preferably each occurrence of M and M² may be the same and may be Ni(ll), Co(ll), Zn(ll) or Mg(ll).

Preferably, the catalyst has a neutral overall charge. It will be appreciated that M and/or M² may each have one or more optional X groups (n and m) co-ordinated to the metal centre depending on the oxidization state of the M and M² metals and on the charge of the Y and Y² groups used, wherein X is as defined above. For example, given that the ligand without the Y groups has a charge of 2-, if each of the metal groups, M and M², are Ni(ll) and each Y group, Y and Y², are anionic (i.e. each have a single negative charge) then the catalyst may have an overall charge of 0. In this case, no additional X groups are co-ordinated to the metal centres. However, if one or both metal centres have a III oxidation state with a charge of 3+ then even if the Y groups are anionic further X groups on each M(lll) are required. For further example, if each of the Y groups is neutral, then the overall ligand has a charge of 2^". If both metal centres are M(ll) then there may be a total of 2 X groups to satisfy the overall neutral charge, if both metal centres are M(lll) then there may be a total of 4 X groups to satisfy the overall neutral charge.

Preferable catalysts of formula (I) are:

22



The catalyst according to the second aspect of the present invention is of formula (II), wherein R -R⁵, R⁹, R ⁰, R ³-R²¹ E , E², E³, X, R^x, G, M and M² of formula (II) are each defined as above in relation to the first aspect of the present invention. Y and Y² of formula (II) are groups which are capable of donating a lone pair of electrons to the metal M² as defined above. The atom of the Y and Y² groups which donates the lone pair of elections typically forms a bond between Y and Y², respectively, and the metal, M². Y and Y² may be the same or different. Preferably, Y and Y² are the same. Y and Y² of formula (II) may independently comprise from 1 to 20 atoms, preferably from 1 to 15 atoms, more preferably from 1 to 10 atoms.

Preferably, Y and Y² of formula (II) may independently be selected from -^~NC(0)R¹⁰, -C(0)N^" R ⁰ , -C0₂ ^~, -C(0)R¹⁰ -C(R ⁰)₂C(O)N^~(R¹⁰), optionally substituted heteroaliphatic wherein at least one heteroatom is nitrogen such as - NR¹⁰, -N(R ⁰)₂, -C(R ⁰)₂N(R ⁰)₂, -C(R ⁰)=N(R¹⁰), or optionally substituted heteroalicyclic wherein at least one heteroatom is nitrogen or an optionally substituted carbene structure such as imidazolylidene, benzimidazolylidene or imidazolinylidene, wherein R ⁰ is independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group. More preferably, Y and Y² may be independently selected from -^~N(R¹⁰), -N(R ⁰)₂, -C(R ⁰)₂N(R ⁰)₂, -C(R ⁰)=N(R¹⁰), -^" NC(0)R¹⁰, or optionally substituted imidazoline, 'abnormal' imidazoline (wherein the 'abnormal' imidazoline has a positive and a negative charge on the heterocycle due to the position of the double bond), imidazolidine, pyrrolidine, pyrroline, triazoline, thiazoline oxazole, oxazoline, imidazoylidene, imidazolinylidene, thiazolylidene, oxazolylidene, triazolylidene, benzimidazolylidene, pyrrolidinylidene, 'abnormal imidazolylidene or N,N'-diamidocarbene, wherein R ⁰ is independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group.

When Y and Y² are independently selected from optionally substituted heteroaliphatic, or heteroalicyclic wherein the at least one heteroatom is nitrogen, the said nitrogen donates the lone pair to the metal M². When Y and Y² are independently selected from an optionally substituted carbene structure, the optionally substituted carbene structure contains a carbon atom that is capable of donating the lone pair to metal M². Still more preferably, Y and Y² of formula (II) may independently be selected from - CH₂N(CH₃)₂, -CH₂N(H)(CH₂CH(CH₃)₂), -CH₌NC(CH₃)₃, -CH=N(CH₂CH(CH₃)₂), -CH₂-piperidine, -CH=NC₆H₃(CH₃)₂, -CH=NCH(CH₃)₂, -CH₂N(C₄H₉)₂, -CH=NC₆H₂(CH₃)₃, -CH₂N(C₂H₅)₂, - C(CH₃)=NCH₂CH(CH₃)₂ , -CH(CH₃)NHCH₂CH(CH₃)₂, -CH₂-pyrrolidine, -CH₂-morpholine, imidazolylidene, 1 -methyl-imidazolylidene, 1 -ethyl-imidazolinylidene , 1 -isopropyl- imidazolylidene, 1 -methyl-benzimidazolylidene wherein in the non-carbene structures the lone pair is provided by the nitrogen and wherein in the carbene structures the Y group is connected via an unsubstituted ring nitrogen and the lone pair is provided by the carbene carbon.

Most preferably, Y and Y² of formula (II) are independently selected from -CH₂N(CH₃)2, - CH₂N(H)(CH₂CH(CH3)2), -CH₌N(CH₂CH(CH₃)₂), or -CH₂-piperidine. The lone pair donating atom of the Y and Y² groups of formula (II) may independently be attached directly to the remainder of the catalyst of formula (II), via a bond to the respective aryl group, or may be attached to the remainder of the catalyst of formula (II) via a linking group attached to the respective aryl group. Preferably, the linking group, when present in Y and/or Y², is selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene. More preferably, the linking group, when present in Y and/or Y², is selected from optionally substituted alkylene, alkenylene, alkynylene or arylene, even more preferably optionally substituted alkylene of arylene. Preferably, the linking group, when present in Y and/or Y², is optionally substituted C^-C_w alkylene, more preferably optionally substituted C^-C₆ alkylene, even more preferably optionally substituted C^-C₄ alkylene, most preferably methylene. For the avoidance of doubt, when the lone pair donating atom of the in Y and/or Y² groups is a carbene carbon, the carbene carbon is not attached directly to the remainder of the catalyst of formula (II). The heteroatom of the Y and Y² groups of formula (II) may be attached to the respective aryl group of the remainder of the catalyst of formula (II) via the linking group, when present, by any suitable number of atoms, preferably 1 to 10 atoms, more preferably 1 to 6 atoms, even more preferably 1 to 4 atoms, most preferably 1 to 2 atoms. It will be appreciated that when the heteroatom of the Y and/or Y² groups is attached directly to the respective aryl group of the remainder of the catalyst of formula (II), no linking group is present.

Preferable catalysts of formula (II) are:

Double metal cyanide (DMC) catalyst The process of the first or third aspects of the present invention may further comprise a double metal cyanide catalyst.

DMC catalysts are complicated compounds which comprise at least two metal centres and cyanide ligands. The DMC catalyst may additionally comprise at least one of: one or more organic complexing agents, water, a metal salt and/or an acid (e.g. in non-stoichiometric amounts).

The first two of the at least two metal centres may be represented by M' and M".

M" may be selected from Zn(ll), Ru(ll), Ru(lll), Fe(ll), Ni(ll), Mn(ll), Co(ll), Sn(ll), Pb(ll), Fe(lll), Mo(IV), Mo(VI), Al(lll), V(V), V(VI), Sr(ll), W(IV), W(VI), Cu(ll), and Cr(lll), M" is preferably selected from Zn(ll), Fe(ll), Co(ll) and Ni(ll), even more preferably M' is Zn(ll). M" is selected from Fe(ll), Fe(lll), Co(ll), Co(lll), Cr(ll), Cr(lll), Mn(ll), Mn(lll), Ir(lll), Ni(ll), Rh(lll), Ru(ll), V(IV), and V(V), preferably M" is selected from Co(ll), Co(lll), Fe(ll), Fe(lll), Cr(lll), Ir(lll) and Ni(ll), more preferably M" is selected from Co(ll) and Co(lll).

It will be appreciated that the above preferred definitions for M' and M" may be combined. For example, preferably M' may be selected from Zn(ll), Fe(ll), Co(ll) and Ni(ll), and M" may preferably selected form be Co(ll), Co(lll), Fe(ll), Fe(lll), Cr(lll), Ir(lll) and Ni(ll). For example, M' may preferably be Zn(ll) and M" may preferably be selected from Co(ll) and Co(lll).

If a further metal centre(s) is present, the further metal centre may be further selected from the definition of M' or M".

Examples of DMC catalysts which can be used in the method of the invention include those described in US 3,427,256, US 5,536,883, US 6,291 ,388, US 6,486,361 , US 6,608,231 , US 7,008,900, US 5,482,908, US 5,780,584, US 5,783,513, US 5,158,922, US 5,693,584, US 7,81 1 ,958, US 6,835,687, US 6,699,961 , US 6,716,788, US 6,977,236, US 7,968,754, US 7,034,103, US 4,826,953, US 4,500 704, US 7,977,501 , US 9,315,622, EP-A-1568414, EP-A- 1529566, and WO 2015/022290, the entire contents of which are incorporated by reference.

DMC catalysts which are useful in the invention may be produced by treating a solution (such as an aqueous solution) of a metal salt with a solution (such as an aqueous solution) of a metal cyanide salt in the presence of one or more organic complexing agents, water, and/or an acid. Suitable metal salts include compounds of the formula M'(X')_P, wherein M' is selected from Zn(ll), Ru(ll), Ru(lll), Fe(ll), Ni(ll), Mn(ll), Co(ll), Sn(ll), Pb(ll), Fe(lll), Mo(IV), Mo(VI), Al(lll), V(V), V(VI), Sr(ll), W(IV), W(VI), Cu(ll), and Cr(lll), and M' is preferably selected from Zn(ll), Fe(ll), Co(ll) and Ni(ll), even more preferably M' is Zn(ll). X' is an anion selected from halide, oxide, hydroxide, sulphate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, preferably X' is halide. p is an integer of 1 or more, and the charge on the anion multiplied by p satisfies the valency of M'. Examples of suitable metal salts include zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetonate, zinc benzoate, zinc nitrate, iron(ll) sulphate, iron (II) bromide, cobalt(ll) chloride, cobalt(ll) thiocyanate, nickel(ll) formate, nickel(ll) nitrate, and mixtures thereof.

Suitable metal cyanide salts include compounds of the formula (Y)q[M"(CN)_b(A)_c], wherein M" is selected from Fe(ll), Fe(lll), Co(ll), Co(lll), Cr(ll), Cr(lll), Mn(ll), Mn(lll), Ir(lll), Ni(ll), Rh(lll), Ru(ll), V(IV), and V(V), preferably M" is selected from Co(ll), Co(lll), Fe(ll), Fe(lll), Cr(lll), Ir(lll) and Ni(ll), more preferably M" is selected from Co(ll) and Co(lll).Y is a proton (H⁺) or an alkali metal ion or an alkaline earth metal ion (such as K⁺), A is an anion selected from halide, oxide, hydroxide, sulphate, cyanide oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, q and b are integers of 1 or more, preferably b is 4 or 6. c may be 0 or an integer of 1 or more. The sum of the charges on the ions Y, CN and A multiplied by q, b and c respectively (e.g. Y x q + CN x b + A x c) satisfies the valency of M". Examples of suitable metal cyanide salts include potassium hexacyanocobaltate(lll), potassium hexacyanoferrate(ll), potassium hexacyanoferrate(lll), calcium hexacyanocobaltate(lll), lithium hexacyanocolbaltate(lll), and mixtures thereof.

Suitable complexing agents include (poly)ethers, polyether carbonates, polycarbonates, poly(tetramethylene ether diol)s, ketones, esters, amides, alcohols, ureas and the like. Exemplary complexing agents inlcude propylene glycol, polypropylene glycol (PPG), (m)ethoxy ethylene glycol, dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyme, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec- butyl alcohol, 3-buten-1 -ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1 -pentyn-3- ol etc. It will be appreciated that the alcohol may be saturated or may contain an unsaturated moiety (e.g. a double or triple bond). Multiple (i.e. more than one different type of) complexing agents may be present in the DMC catalysts used in the present invention.

The DMC catalyst may comprise a complexing agent which is a polyether, polyether carbonate or polycarbonate. Suitable polyethers for use in the present invention include those produced by ring-opening polymerisation of cyclic ethers, and include epoxide polymers, oxetane polymers, tetrahydrofuran polymers, and the like. Any method of catalysis can be used to make the polyethers. The polyethers can have any desired end groups, including, for example, hydroxyl, amine, ester, ether, or the like. Preferred polyethers for use in the present invention are polyether polyols having between 2 and 8 hydroxyl groups. It is also preferred that polyethers for use in the present invention have a molecular weight between about 1 ,000 Daltons and about 10,000 Daltons, more preferably between about 1 ,000 Daltons and about 5,000 Daltons. Polyether polyols useful in the DMC catalyst of the present invention include PPG polyols, EO- capped PPG polyols, mixed EO-PO polyols, butylene oxide polymers, butylene oxide copolymers with ethylene oxide and/or propylene oxide, polytetramethylene ether glycols, and the like. Preferred polyethers include PPGs, such as PPG polyols, particularly diols and triols, said PPGs having molecular weights of from about 250 Daltons to about 8,000 Daltons, more preferably from about 400 Daltons to about 4,000 Daltons.

Suitable polyether carbonates for use in the DMC catalyst of the present invention may be obtained by the catalytic reaction of alkylene oxides and carbon dioxide in the presence of a suitable starter or initiator compound. The polyether carbonates used as the complexing agent can also be produced by other methods known to the person skilled in the art, for example by partial alcoholysis of polycarbonate polyols with di- or tri-functional hydroxy compounds. The polyether carbonates used as the complexing agent preferably have an average hydroxyl functionality of 1 to 6, more preferably 2 to 3, most preferably 2.

Suitable polycarbonates for use in the DMC catalyst of the present invention may be obtained by the polycondensation of difunctional hydroxy compounds (generally bis-hydroxy compounds such as alkanediols or bisphenols) with carbonic acid derivatives such as, for example, phosgene or bis[chlorocarbonyloxy] compounds, carbonic acid diesters (such as diphenyl carbonate or dimethyl carbonate) or urea. Methods for producing polycarbonates are generally well known and are described in detail in for example "Houben-Weyl, Methoden der organischen Chemie", Volume E20, Makromolekulare Stoffe, 4^th Edition, 1987, p. 1443-1457, "Ullmann's Encyclopedia of Industrial Chemistry", Volume A21 , 5^th Edition, 1992, p. 207-215 and "Encyclopedia of Polymer Science and Engineering", Volume 1 1 , 2^nd Edition, 1988, p. 648-718. Aliphatic polycarbonate diols having a molecular weight of from about 500 Daltons to 5000 Daltons, most highly preferably from 1000 Daltons to 3000 Daltons, are particularly preferably used. These are generally obtained from non-vicinal diols by reaction with diaryl carbonate, dialkyl carbonate, dioxolanones, phosgene, bischloroformic acid esters or urea (see for example EP-A 292 772 and the documents cited therein). Suitable non-vicinal diols are in particular 1 ,4-butanediol, neopentyl glycol, 1 ,5-pentanediol, 2-methyl-1 ,5-pentanediol, 3- methyl-1 ,5-pentanediol, 1 ,6-hexanediol, bis-(6-hydroxyhexyl)ether, 1 ,7-heptanediol, 1 ,8- octanediol, 2-methyl-1 ,8-octanediol, 1 ,9-nonanediol, 1 ,10-decanediol, 1 ,4-bis-hydroxymethyl cyclohexane, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, alkoxylation products of diols with ethylene oxide and/or propylene oxide and/or tetrahydrofuran with molar masses up to 1000 Daltons, preferably between 200 Daltons and 700 Daltons, and in rarer cases the dimer diols, which are obtainable by reducing both carboxyl groups of dimer acids, which in turn can be obtained by dimerisation of unsaturated vegetable fatty acids. The non-vicinal diols can be used individually or in mixtures. The reaction can be catalysed by bases or transition metal compounds in the manner known to the person skilled in the art.

Other complexing agents that may be useful in present invention include poly(tetramethylene ether diols). Poly(tetramethylene ether diols) are polyether polyols based on tetramethylene ether glycol, also known as polytetrahydrofuran (PTHF) or polyoxybutylene glycol. These poly(tetramethylene ether diols) comprise two OH groups per molecule. They can be produced by cationic polymerisation of tetrahydrofuran (THF) with the aid of catalysts.

Complexing agents, as defined above, may be used to increase or decrease the crystallinity of the resulting DMC catalyst. Suitable acids for use in the DMC catalyst of the present invention may have the formula H_rX"', where X'" is an anion selected from halide, sulfate, phosphate, borate, chlorate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, preferably X'" is a halide. r is an integer corresponding to the charge on the counterion X'". For example, when X'" is CI^", r will be 1 , i.e. the salt will be HCI.

If present, particularly preferred acids for use in the DMC catalyst of the present invention having the formula H_rX"' include the following: HCI, H₂S0₄, HN0₃, H₃P0₄, HF, HI, HBr, H₃B0₃ and HCI0₄. HCI, HBr and H₂S0₄ are particularly preferred. It will also be appreciated that an alkali metal salt (e.g. an alkali metal hydroxide such as KOH, an alkali metal oxide or an alkali metal carbonate) may be added to the reaction mixture during synthesis of the DMC catalyst. For example, the alkali metal salt may be added to the reaction mixture after the metal salt (M'(X')_P) has been added to the metal cyanide salt ((Y)q[M"(CN)_b(A)_c]).

In one common preparation, an aqueous solution of zinc chloride (excess) is mixed with an aqueous solution of potassium hexacyanocobaltate, and an organic complexing agent (such as dimethoxyethane or tert-butyl alcohol) is added to the resulting slurry. After filtration and washing of the catalyst with an aqueous solution of the complexing agent (e.g. aqueous dimethoxyethane or aqueous tert-butyl alcohol), an active catalyst is obtained. Subsequent washing step(s) may be carried out using just the complexing agent, in order to remove excess water. Each one is followed by a filtration step. In an alternative preparation, several separate solutions may be prepared and then combined in order. For example, the following solutions may be prepared:

1 . a solution of a metal cyanide (e.g. potassium hexacyanocobaltate)

2. a solution of a metal salt e.g. (zinc chloride (excess))

3. a solution of a first complexing agent (e.g. PPG diol)

4. a solution of a second complexing agent (e.g. tert-butyl alcohol).

In this method, solutions 1 and 2 are combined immediately, followed by slow addition of solution 4, preferably whilst stirring rapidly. Solution 3 may be added once the addition of solution 4 is complete, or shortly thereafter. The catalyst is removed from the reaction mixture via filtration, and is subsequently washed with a solution of the complexing agents.

If water is desired in the DMC catalyst, then the above solutions (e.g. solutions 1 to 4) may be aqueous solutions. However, it will be understood that anhydrous DMC catalysts (i.e. DMC catalysts without any water present) may be prepared if the solutions described in the above preparations are anhydrous solutions. To avoid hydrating the DMC catalyst and thereby introducing water molecules, any further processing steps (washing, filtration etc.) may be conducted using anhydrous solvents.

In one common preparation, several separate solutions may be prepared and then combined in order. For example, the following solutions may be prepared:

1 . a solution of a metal salt (e.g. zinc chloride (excess)) and a second complexing agent (e.g. tert-butyl alcohol)

2. a solution of a metal cyanide (e.g. potassium hexacyanocobaltate)

3. a solution of a first and a second complexing agent (e.g. the first complexing agent may be a polymer (for example, PPG diol) and the second complexing agent may be tert-butyl alcohol). In this method, solutions 1 and 2 are combined slowly (e.g. over 1 hour) at a raised temperature (e.g. above 25°C, such as about 50 °C) while stirring (e.g. at 450 rpm). After addition is complete the stirring rate is increased for 1 hour (e.g. up to 900 rpm). The stirring rate is then decreased to a slow rate (e.g. to 200 rpm) and solution 3 is added quickly with low stirring. The mixture is filtered.

The catalyst solids may be re-slurried in a solution of the second complexing agent at high stirring rate (e.g. about 900 rpm) before addition of the first complexing agent at low stirring rate (e.g. 200 rpm). The mixture is then filtered. This step may be repeated more than once. The resulting catalyst cake may be dried under vacuum (with heating e.g. to 60 °C). Alternatively, after the mixture is first filtered it can be re-slurried at a raised temperature (e.g. above 25°C, such as about 50 °C) in a solution of the first complexing agent (and no second or further complexing agent) and then homogenized by stirring. It is then filtered after this step. The catalyst solids are then re-slurried in a mixture of the first and second complexing agents. For example, the catalyst solids are re-slurried in the second complexing agent at a raised temperature (e.g above 25°C, such as about 50 °C) and subsequently the first complexing agent is added and mixture homogenized by stirring. The mixture is filtered and the catalyst is dried under vacuum with heating (e.g. to 100 °C).

It will be appreciated that the DMC catalyst may comprise:

M'_d[M"e(CN)_f]_g wherein M' and M" are as defined above, d, e, f and g are integers, and are chosen to such that the DMC catalyst has electroneutrality. Preferably, d is 3. Preferably, e is 1 . Preferably f is 6. Preferably g is 2. Preferably, M' is selected from Zn(ll), Fe(ll), Co(ll) and Ni(ll), more preferably M' is Zn(ll). Preferably M" is selected from Co(lll), Fe(lll), Cr(lll) and Ir(lll), more preferably M" is Co(lll). It will be appreciated that any of these preferred features may be combined, for example, d is 3, e is 1 , f is 6 and g is 2, M' is Zn(ll) and M" is Co(lll).

Suitable DMC catalysts of the above formula may include zinc hexacyanocobaltate(lll), zinc hexacyanoferrate(lll), nickel hexacyanoferrate(ll), and cobalt hexacyanocobaltate(lll).

There has been a lot of development in the field of DMC catalysts, and the skilled person will appreciate that the DMC catalyst may comprise, in addition to the formula above, further additives to enhance the activity of the catalyst. Thus, while the above formula may form the "core" of the DMC catalyst, the DMC catalyst may additionally comprise stoichiometric or non- stoichiometric amounts of one or more additional components, such as at least one organic complexing agent, an acid, a metal salt, and/or water.

For example, the DMC catalyst may have the following formula:

M'_d[M"e(CN)_f]g ^■ hM'"X"i ^■ jR^c■ kH_zO ^■ IH_rX"' wherein M', M", X'", d, e, f and g are as defined above. M'" can be M' and/or M". X" is an anion selected from halide, oxide, hydroxide, sulphate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, preferably X" is halide. i is an integer of 1 or more, and the charge on the anion X" multiplied by i satisfies the valency of M"\ r is an integer that corresponds to the charge on the counterion X'". For example, when X'" is CI^", r will be 1 . 1 is 0, or a number between 0.1 and 5. Preferably, I is between 0.15 and 1 .5.

R^c is a complexing agent, and may be as defined above. For example, R^c may be a (poly)ether, a polyether carbonate, a polycarbonate, a poly(tetramethylene ether diol), a ketone, an ester, an amide, an alcohol (e.g. a C_1-8 alcohol), a urea and the like, such as propylene glycol, polypropylene glycol, (m)ethoxy ethylene glycol, dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyme, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, 3-buten-1 -ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1 -pentyn-3-ol, for example, R^c may be tert-butyl alcohol, dimethoxyethane, or polypropylene glycol.

As indicated above, more than one complexing agent may be present in the DMC catalysts used in the present invention. A combination of the complexing agents tert-butyl alcohol and polypropylene glycol is particularly preferred.

It will be appreciated that if the water, complexing agent, acid and/or metal salt are not present in the DMC catalyst, h, j, k and/or I will be zero respectively. If the water, complexing agent, acid and/or metal salt are present, then h, j, k and/or I are a positive number and may, for example, be between 0 and 20. For example, h may be between 0.1 and 4. j may be between 0.1 and 6. k may be between 0 and 20, e.g. between 0.1 and 10, such as between 0.1 and 5. 1 may be between 0.1 and 5, such as between 0.15 and 1 .5.

As set out above, DMC catalysts are complicated structures, and thus, the above formula including the additional components is not intended to be limiting. Instead, the skilled person will appreciate that this definition is not exhaustive of the DMC catalysts which are capable of being used in the invention.

An exemplary DMC catalyst is of the formula Zn₃[Co(CN)₆]₂ ^■ hZnCI₂ ^■ kH₂0 ^■ j[(CH₃)₃COH], wherein h, k and I are as defined above. For example, h may be from 0 to 4 (e.g. from 0.1 to 4), k may be from 0 to 20 (e.g. from 0.1 to 10), and j may be from 0 to 6 (e.g. from 0.1 to 6).

Chain Transfer Agent

The polymerisation process of the first aspect of the present invention is carried out in the presence of a chain transfer agent. The polymerisation process of the third aspect of the present invention may optionally be carried out in the presence of a chain transfer agent.

Preferably, the chain transfer agent is selected from water or a compound of formula (III): ^Z~(-^W)a

formula (III) wherein Z is an optionally substituted moiety selected from the group consisting of aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, polyolefin, polyester, polyether, polycarbonate or combinations thereof;

each W is independently selected from a hydroxyl, amine, thiol or carboxylate group; and a is an integer which is at least 2. It has surprisingly and advantageously been found by the present inventors that the catalysts of formulae (I) and (II) of the present invention are surprisingly active in the presence of the chain transfer agents. For example, it has been surprisingly and advantageously been found by the present inventors that the catalysts of formulae (I) and (II) of the present invention are not deactivated by chain transfer agents. Without being bound by theory, it would be expected that a polymerisation catalyst having an open cage structure around a bimetallic centre would be more susceptible to catalyst poisoning by the chain transfer agents compared to those catalysts having a closed cage structure around a bimetallic centre. This would result in reduced activity of catalysts having an open cage structure around a bimetallic centre compared to those catalysts having a closed cage structure around a bimetallic centre. However, the catalysts of formula (I), formula (la) and (II) of the present invention surprisingly show and retain good activity during the polymerisation process.

The chain transfer agent (CTA) may be water or a compound which has two or more groups independently selected from hydroxyl (-OH), amine (-NHR^W), thiol (-SH) or carboxylate (- C(O)OH), wherein R^w is hydrogen, optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl, or combinations thereof (i.e. aliphaticaryl, aliphaticheteroaryl, heteroaliphaticaryl, etc). It will be appreciated that although water does not have two distinct "- OH" groups, it displays similar chain transfer properties to molecules which do have two distinct "-OH" groups and is therefore intended to be encompassed by the term "chain transfer agent".

Z is the core of the chain transfer agent any may be any group which can have two or more "W" groups attached to it. In preferred embodiments, Z is an optionally substituted moiety selected from the group consisting of aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, polyolefin, polyester, polyether, polycarbonate or combinations thereof. For example, Z may be an optionally substituted araliphatic, heteroaraliphatic, aliphaticalicyclic etc. group. Preferably, Z is selected from alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or polyether. When Z is a polymer (i.e. when Z comprises a polyolefin, polyester, polyether or polycarbonate group), the molecular weight (Mn) of such polymers are preferably less than 10,000 g/mol. Preferred polymers include poly(ethylene glycol) (PEG) and poly(lactic acid) (PLA).

The chain transfer agent, in particular the group Z, may optionally be substituted. In certain embodiments, Z is optionally substituted by halogen, nitrile, imine, nitro, aliphatic, acetyl, amido, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl. a is an integer which is at least 2. Preferably, a is an integer selected from 2 to 10 inclusive. More preferably, a is an integer selected from 2 to 6 inclusive.

Each occurrence of W may be the same or different. Preferably, each occurrence of W is the same. In certain embodiments, each occurrence of W is hydroxyl (i.e. the chain transfer agent is a polyol, for example a diol, a triol, a tetraol etc.). In other embodiments, each occurrence of W is amine (i.e. the chain transfer agent is a polyamine, for example a diamine, a triamine, a tetraamine etc.). In other embodiments, each occurrence of W is carboxylic acid (i.e. the chain transfer agent is a polycarboxylic acid, for example a diacid, a triacid, a tetraacid etc.). In other embodiments, each occurrence of W is thiol (i.e. the chain transfer agent is a polythiol, for example a dithol, a trithiol, a tetrathiol etc.). In other embodiments, the chain transfer agent is water.

When the chain transfer agent is water, X is preferably not OCOCH₃, OCOCF₃, OSO2C7H7, OSO(CH₃)₂, or halide, more preferably C X is not OCOCH₃, OCOCF₃, OSO2C7H7, OSO(CH₃)₂, halide, alkyl, alkoxy or amido.

A single chain transfer agent may be used or a mixture of chain transfer agents may be used.

Examples of chain transfer agents useful in the first or third aspect include water, mono- alcohols (i.e. alcohols with one OH group, for example, 4-ethylbenzenesulfonic acid, methanol, ethanol, propanol, butanol, pentanol, hexanol, phenol, cyclohexanol), diols (for example, 1 ,2- ethanediol, 1 -2-propanediol, 1 ,3-propanediol, 1 ,2-butanediol, 1 -3-butanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,2-diphenol, 1 ,3-diphenol, 1 ,4-diphenol, catechol and cyclohexenediol), triols (glycerol, benzenetriol, 1 ,2,4-butanetriol, tris(methylalcohol)propane, tris(methylalcohol)ethane, tris(methylalcohol)nitropropane, trimethylolpropane, preferably glycerol or benzenetriol), tetraols (for example, calix[4]arene, 2, 2-bis(methylalcohol)-1 ,3- propanediol, di(trimethylolpropane)), polyols (for example, dipentaerythritol, D-(+)-glucose or D-sorbitol), dihydroxy terminated polyesters (for example polylactic acid), dihydroxy terminated polyethers (for example poly(ethylene glycol)), acids (such as diphenylphosphinic acid), starch, lignin, mono-amines (i.e. methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine), diamines (for examplel ,4-butanediamine), triamines, diamine terminated polyethers, diamine terminated polyesters, mono-carboxylic acids (for example, 3,5-di-tert-butylbenzoic acid), dicarboxylic acids (for example, maleic acid, malonic acid, succinic acid, glutaric acid or terephthalic acid, preferably maleic acid, malonic acid, succinic acid, glutaric acid), tricarboxylic acids (for example, citric acid, 1 ,3,5-benzenetricarboxylic acid or 1 ,3,5-cyclohexanetricarboxylic acid, preferably citric acid), mono-thiols, dithoils, trithiols, and compounds having a mixture of hydroxyl, amine, carboxylic acid and thiol groups, for example lactic acid, glycolic acid, 3-hydroxypropionic acid, natural amino acids, unnatural amino acids, monosaccharides, disaccharides, oligosaccharides and polysaccharides (including pyranose and furanose forms). Preferably, the chain transfer agent is selected from cyclohexene diol, 1 ,2,4-butanetriol, tris(methylalcohol)propane, tris(methylalcohol)nitropropane, tris(methylalcohol)ethane, tri(methylalcohol)propane, tri(methylalcohol)butane, pentaerythritol, poly(propylene glycol), glycerol, mono- and di- ethylene glycol, propylene glycol, 2,2-bis(methylalcohol)-1 ,3-propanediol, 1 ,3,5- benzenetricarboxylic acid, 1 ,3,5-cyclohexanetricarboxylic acid, 1 ,4-butanediamine, 1 ,6- hexanediol, D-sorbitol, 1 -butylamine, terephthalic acid, D-(+)-glucose, 3,5-di-tert-butylbenzoic acid, and water.

In certain embodiments, the chain transfer agent is not water. In alternative embodiments, the chain transfer agent is water. It was found that both the metal centres and the ligand set of the catalysts used in the process of the first or third aspect are surprisingly hydrolytically stable (i.e. do not degrade in the presence of water). Water functions extremely well as a chain transfer agent for the polymerisation process of the present invention and is cheap and readily available. Furthermore, it is not necessary to ensure that all reagents, such as monomers (including the carbon dioxide) and solvents are entirely free of water before beginning the reaction. This avoids lengthy and costly purification steps of reagents such as carbon dioxide, which are frequently contaminated with water (particularly carbon dioxide captured from industrial sources). In fact, impurities in the monomers, solvents etc. can provide the entire amount of chain transfer agent necessary to convert all of the end groups of the polymer products produced by the first and third aspects of the present invention to hydroxyl groups.

The chain transfer agent may be present in a molar ratio of at least 1 :1 relative to the metal complex (catalyst of formula (I) or (II)). Preferably, the chain transfer agent may be present in a molar ratio of between about 1 :1 to about 100:1 relative to the metal complex. More preferably, the chain transfer agent may be present in a molar ratio from 1 :1 to 9:1 . Most preferably, the chain transfer agent may be present in a molar ratio of at least 2:1 relative to the metal complex. A halogenated X group reduces the amount of chain transfer agent required to produce polycarbonate chains which are terminated at both ends with hydroxyl groups. In fact, water impurities which are present either in the carbon dioxide or left over from the production of the catalyst (for example, if hydrated metal acetates are used to produce the catalysts useful in the first and third aspect), can act as a sufficient amount of chain transfer agent (where the chain transfer agent is water) to ensure that all polycarbonate chains are terminated in hydroxyl groups. An excess of chain transfer agent is not therefore required. Therefore in certain embodiments, X is a halogenated group and the chain transfer agent:metal complex molar ratio is at least 0.1 :1 , preferably at least 1 :1 , more preferably 0.1 :1 to 9:1 , even more preferably 0.1 :1 to 1 :1 . Preferably X is OC(0)Rx, OS02Rx, OSO(Rx)2, ORx, or haloaliphatic, wherein one or both Rx groups are haloaliphatic, haloaryl or haloalicyclic more preferably haloaliphatic (such as fluoroaliphatic). The chain transfer agent may be used to control the molecular weight (M_n) of the polymers produced by the process of the first and third aspect.

Reactants

When the polymerisation process of the first and third aspects of the present invention comprises the reaction of carbon dioxide with an epoxide and/or the reaction of an anhydride with an epoxide, the epoxide may be any compound comprising an epoxide moiety. The epoxide may be on a group which is aliphatic including acyclic and alicyclic or aromatic. Examples of epoxides which may be used in the present invention include, but are not limited to, cyclohexene oxide, styrene oxide, unsubstituted or substituted alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, substituted cyclohexene oxides (such as limonene oxide, C ₀H ₆O or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C h^O), unsubstituted or substituted oxiranes (such as oxirane, epichlorohydrin, 2-(2- methoxyethoxy)methyl oxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyl oxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl oxirane (ME3MO), 1 ,2- epoxybutane, glycidyl ethers, vinyl-cyclohexene oxide, 3-phenyl-1 ,2-epoxypropane, 1 ,2- and 2,3-epoxybutane, isobutylene oxide, cyclopentene oxide, 2,3-epoxy-1 ,2,3,4- tetrahydronaphthalene, indene oxide, and functionalized 3,5-dioxaepoxides. Examples of functionalized 3,5-dioxaepoxides include:

The epoxide moiety may be a glycidyl ether, glycidyl ester or glycidyl carbonate. Examples of glycidyl ethers, glycidyl esters glycidyl carbonates include:

The epoxide substrate may contain more than one epoxide moiety, i.e. it may be a bis- epoxide, a tris-epoxide, or a multi-epoxide containing moiety. Examples of compounds including more than one epoxide moiety include bisphenol A diglycidyl ether and 3,4- epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. It will be understood that reactions carried out in the presence of one or more compounds having more than one epoxide moiety may lead to cross-linking in the resulting polymer.

The skilled person will appreciate that the epoxide can be obtained from "green" or renewable resources. The epoxide may be obtained from a (poly)unsaturated compound, such as those deriving from a fatty acid and/or terpene, obtained using standard oxidation chemistries. The epoxide moiety may contain -OH moieties, or protected -OH moieties. The -OH moieties may be protected by any suitable protecting group. Suitable protecting groups include methyl or other alkyl groups, benzyl, allyl, tert-butyl, tetrahydropyranyl (THP), methoxymethyl (MOM), acetyl (C(O)alkyl), benzolyl (C(O)Ph), dimethoxytrityl (DMT), methoxyethoxymethyl (MEM), p- methoxybenzyl (PMB), trityl, silyl (such as trimethylsilyl (TMS), f-Butyldimethylsilyl (TBDMS), t- Butyldiphenylsilyl (TBDPS), tri-/^'so-propylsilyloxymethyl (TOM), and triisopropylsilyl (TIPS)), (4- methoxyphenyl)diphenylmethyl (MMT), tetrahydrofuranyl (THF), and tetrahydropyranyl (THP).

The epoxide may be purified (for example by distillation, such as over calcium hydride) prior to reaction with carbon dioxide or anhydride. For example, the epoxide may be distilled prior to being added to the reaction mixture comprising the catalyst of formula (I) or (II).

The epoxide preferably has a purity of at least 98%, more preferably >99%. It will be understood that the term "an epoxide" is intended to encompass one or more epoxides. In other words, the term "an epoxide" refers to a single epoxide, or a mixture of two or more different epoxides. For example, the epoxide substrate may be a mixture of ethylene oxide and propylene oxide, a mixture of cyclohexene oxide and propylene oxide, a mixture of ethylene oxide and cyclohexene oxide, or a mixture of ethylene oxide, propylene oxide and cyclohexene oxide.

The skilled person will also understand that substituted and unsubstituted oxetanes can be used in place of, and in addition to, the epoxides of the first or third aspect of the invention. Suitable oxetanes include unsubstituted or substituted oxetanes (preferably substituted at the 3-position by halogen, alkyl (unsubstituted or substituted by -OH or halogen), amino, hydroxyl, aryl (e.g. phenyl), alkylaryl (e.g. benzyl)). Exemplary oxetanes include oxetane, 3-ethyl-3- oxetanemethanol, oxetane-3-methanol, 3-methyl-3-oxetanemethanol, 3-methyloxetane, 3- ethyloxetane, etc. It has surprisingly and advantageously been found by the present inventors that the catalysts of formulae (I) and (II) of the present invention have activity for propylene oxide and other mono-substituted epoxides. It will be known to a person skilled in the art that many catalysts that are active in the polymerisation of cyclohexene oxide and its derivatives are not active in the polymerisation of unsubstituted or monosubstituted epoxides such as propylene oxide.

Preferably, the epoxide may be on a group which is acyclic. Preferably, the epoxide may be a C -C ₀ alkyl oxide. More preferably, the epoxide may be ethylene oxide, propylene oxide, butylene oxide or a combination thereof. Most preferably, the epoxide may be ethylene oxide, propylene oxide or a combination thereof. Such oxides are of special interest as they produce polymers (polyalkylene carbonates, such as PPC) with elastomeric properties which are useful in many applications e.g. films.

When the polymerisation process of the first and third aspects of the present invention comprises the reaction of an anhydride with an epoxide, the anhydride may be any compound comprising an anhydride moiety in a ring system (i.e. a cyclic anhydride). The epoxide may be any of the epoxides described above. Preferably, the anhydrides which are useful in the present invention have the following formula:

Wherein m" is 1 , 2, 3, 4, 5, or 6 (preferably 1 or 2), each R^a , R^a2, R^a3 and R^a4 is independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl; or two or more of R , R , R and R can be taken together to form a saturated, partially saturated or unsaturated 3 to 12 membered, optionally substituted ring system, optionally containing one or more heteroatoms, or can be taken together to form a double bond. Each Q is independently C, O, N or S, preferably C, wherein R^a3 and R^a4 are either present, or absent, and can either be = or , according to the valency of Q. It will be appreciated that when Q is C, and is , R^a3 and R^a4 (or two R^a4 on adjacent carbon atoms) are absent.

The skilled person will appreciate that the anhydrides may be obtained from "green" or renewable resources.

Preferable anhydrides are set out below.

Reaction Conditions

The polymerisation process of the first and third aspects of the present invention may be carried out at any suitable pressure. The polymerisation process may be carried out at a pressure of 1 to 100 atmospheres, preferably at 1 to 40 atmospheres, such as at 1 to 20 atmospheres, more preferably at 1 or 10 atmospheres. The catalysts of formula (I) and (II) used in the polymerisation process allow the reaction to be carried out at low pressures. For example, the catalysts of formula (I) and (II) allow the reaction to be carried out at low pressure such as 1 atmosphere. However, for the avoidance of doubt, the catalysts of formula (I) and (II) are also active at much higher pressures, such as 40 atmospheres. Indeed, the catalysts of formula (I) and (II) show comparable turnover number (TON) and turnover frequency (TOF) to literature catalysts but operate at 1 /60 of the pressure.

The polymerisation process may be carried out at any suitable temperature. The polymerisation process may be carried out at a temperature of about 0°C to about 250°C, preferably from about 40°C to about 160°C, even more preferably from about 50°C to about 120°C.

The duration of the polymerisation process may be up to 168 hours, preferably from about 1 minute to about 24 hours, more preferably from about 5 minutes to about 12 hours, most preferably from about 1 to about 6 hours.

When the polymerisation process comprises the reaction of carbon dioxide with an epoxide, the process temperature (i.e. the temperature at which the polymerisation process is carried out) may be used to control the product composition. When the temperature is increased, the selectivity of the catalyst of formula (I) and (II) towards the formation of cyclic carbonate is also increased. The catalysts of formula (I) and (II) and polymerisation processes may operate at temperatures of up to 250°C.

The polymerisation process may be carried out at low catalytic loading. For example, when the polymerisation comprises the reaction of carbon dioxide with an epoxide, the catalytic loading for the process is preferably about 1 :1 ,000-100,000 catalyst:epoxide, more preferably about 1 :1 ,000-300,000 catalyst:epoxide, even more preferably about 1 :10,000-100,000, and most preferably about 1 :50,000-100,000 catalyst:epoxide. When the polymerisation process comprises the reaction of an anhydride with an epoxide the catalytic loading for the process is preferably about 1 :1 ,000-300,000 catalyst:total monomer content, more preferably about 1 :10,000-100,000 catalyst:total monomer content, most preferably about 1 :50,000-100,000 catalyst:total monomer content. For the avoidance of doubt, the ratios above are molar ratios.

The ratio of the catalyst of formula (I) and (II) to the DMC catalyst may be in the range of from about 300:1 to about 0.1 :1 , for example, from about 120:1 to about 0.25:1 , such as from about 40:1 to about 0.5:1 , e.g. from about 30:1 to about 0.75:1 such as from about 20:1 to about 1 :1 , for example from about 10:1 to about 2:1 , e.g. from about 5:1 to about 3:1 . These ratios are mass ratios. The starter compound may be present in amounts of from about 200:1 to about 1 :1 , for example, from about 175:1 to about 5:1 , such as from about 150:1 to about 10:1 , e.g. from about 125:1 to about 20:1 , for example, from about 50:1 to about 20:1 , relative to the catalyst of formula (I) and (II). These ratios are molar ratios.

The polymerisation process may be carried out in the presence of a solvent. Examples of solvents useful in the first or third aspect include toluene, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, methylene chloride, propylene carbonate, ethylene carbonate, etc.

The polymerisation process can be carried out in a batch reactor or a continuous reactor.

Products

The polymer products of the polymerisation process of the first and third aspects of the present invention may be polycarbonates, polyether carbonate polyols or polyester polyols. For example, the polymer products may be polyether carbonate polyols such as poly(cyclohexene carbonate) (PCHC) or polypropylene carbonate) (PPC). It will be understood, therefore, that the polymer of the fourth aspect of the present invention may also be a polycarbonate, polyether carbonate polyol or a polyester polyol. Reference herein to 'polymer products' includes the products of the polymerisation process of the first and third aspects of the present invention and the polymer of the fourth aspect of the present invention. It will be appreciated that when the polymerisation process of the first and third aspects is the reaction of carbon dioxide with an epoxide, the polymer product may be a polycarbonate or a polyether carbonate polyol. When the polymerisation process of the first and third aspects is the reaction of an anhydride with an epoxide the polymer product is a polyester polyol.

When the polymer products are polyether carbonate polyols, the polyether carbonate polyols may have n ether linkages and m carbonate linkages, wherein n and m are integers, and wherein m/(n+m) is from greater than zero to less than 1 . When the polymer products are polycarbonates, the polycarbonates may have n ether linkages and m carbonate linkages, wherein n and m are integers, and wherein m/(n+m) is equal to 1 . Therefore, it will be appreciated by a person skilled in the art that when m/(n+m) is 1 , the polymer product is a polycarbonate and when m/(n+m) is from greater than zero to less than 1 , the polymer product is a polyether carbonate polyol.

Typically, when the polymerisation process of the first or third aspects of the present invention are carried out in the presence of a DMC catalyst, as described above, the ratio of m/(n+m) is from more than 0 to less than 1 . Typically, when the polymerisation process of the first or third aspects of the present invention are carried out in the absence of a DMC catalyst, as described above, i.e. in the presence of a catalyst of formula (I) or (II) only, the ratio of m/(n+m) is from 0.05 to 0.95.

For example, the polymerisation process of the invention is capable of preparing polycarbonates having an m/(n+m) value equal to 1 . A person skilled in the art will appreciate that in this case, the epoxide and C0₂ monomers of the polymer product are fully alternating.

For example, the polymerisation process of the invention is capable of preparing polyether carbonate polyols having a wide range of m/(n+m) values. m/(n+m) may be <0.05, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, >0.95 or within any range prepared from the specific examples. For example, m/(n+m) may be from about 0.5 to 0.95, from about 0.10 to 0.90, from about 0.15 to 0.85, from about 0.20 to about 0.80 or from about 0.25 to about 0.75 etc. In certain embodiments, when polymer products are polyether carbonate polyols, the polyether carbonate polyols may have a high proportion of carbonate linkages, for example m/(n+m) may be greater than about 0.50, such as from greater than about 0.55 to less than about 0.95, for example about 0.65 to about 0.90, for example about 0.75 to about 0.90. The polymerisation process of the first and third aspects of the present invention is able to prepare polyether carbonate polyols having a high ratio of m/(n+m) under mild conditions, for example, under pressures of 20 atmospheres or below, such as 10 atmospheres or below. The polyether carbonate polyols may have a structure according to formula (IV):

formula (IV) wherein Z and W depend on the nature of the chain transfer agent, R' and R" depend on the nature of the epoxide and m and n define the amount of the carbonate and polyether linkages in the polyether carbonate polyol. It will be appreciates that the polyether carbonate polyol must contain at least one carbonate and at least one ether linkage. Therefore it will be appreciated that the number of ether and carbonate linkages (n+m) in the polyol will be greater than or equal to a. The sum of n+m must be greater than or equal to a.

It will be appreciated that in the polymers of formula (IV), the adjacent epoxide monomer units in the backbone may be head-to-tail linkages, head-to-head linkages or tail-to-tail linkages. It will also be appreciated that formula (III) does not require the carbonate links and the ether links to be present in two distinct "blocks" in each of the sections defined by "a", but instead the carbonate and ether repeating units may be statistically distributed along the polymer backbone, or may be arranged so that the carbonate and ether linkages are not in two distinct blocks.

Thus, the polyether carbonate polyol (e.g. a polymer of formula (IV)) may be referred to as a random copolymer, a statistical copolymer, an alternating copolymer, or a periodic copolymer. It will be appreciated that the wt% of carbon dioxide incorporated into a polymer cannot be definitively used to determine the amount of carbonate linkages in the polymer backbone. For example, two polymers which incorporate the same wt% of carbon dioxide may have very different ratios of carbonate to ether linkages. This is because the "wt% incorporation" of carbon dioxide does not take into account the length and nature of the chain transfer agent. For instance, if one polymer (Mn 2000 g/mol) is prepared using a chain transfer agent with a molar mass of 100 g/mol, and another polymer (Mn also 2000 g/mol) is prepared using a chain transfer having a molar mass of 500 g/mol, and both the resultant polymers have the same ratio of m/n then the wt% of carbon dioxide in the polymers will be different due to the differing proportion of the mass of the chain transfer agent in the overall polymer molecular weight (Mn). For example, if m/(m+n) was 0.5, the two polyether carbonate polyols described would have carbon dioxide contents of 26.1 wt% and 20.6 wt% respectively. As highlighted above, the polymerisation process of the first and third aspects of the present invention is able to produce polyether carbonate polyols which have a wide range of carbonate to ether linkages (e.g. m/(n+m) can be from greater than zero to 1), which, when using propylene oxide, corresponds to incorporation of up to about 43 wt% carbon dioxide. Similarly, polycarbonates can be formed wherein m/(n+m) is 1 .

As set out above, the method of the polymerisation process of the first and third aspects of the present invention is able to produce polyether carbonate polyols which are a random copolymer, a statistical copolymer, an alternating copolymer, or a periodic copolymer. Thus, the carbonate linkages are not in a single block, thereby providing a polymer product which has improved properties, such as improved thermal degradation, as compared to a polycarbonate polyol. Preferably, the polymer prepared by the method of the invention is a random copolymer or a statistical copolymer.

Each R' may independently be selected from H, halogen, hydroxyl, or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyi, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group. Preferably R' may be selected from H or optionally substituted alkyl. Each R" may independently be selected from H, halogen, hydroxyl, or or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyi, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group. Preferably R" may be selected from H or optionally substituted alkyl.

R' and R" may together form a saturated, partially unsaturated or unsaturated ring containing carbon and hydrogen atoms, and optionally one or more heteroatoms (e.g. O, N or S). For example, R' and R" may together form a 5 or six membered ring.

As set out above, the nature of R' and R" will depend on the epoxide used in the reaction. If the epoxide is cyclohexene oxide (CHO), then R' and R" will together form a six membered alkyl ring (e.g. a cyclohexyl ring). If the epoxide is ethylene oxide, then R' and R" will both be H. If the epoxide is propylene oxide, then R' will be H and R" will be methyl (or R' will be methyl and R" will be H, depending on how the epoxide is added into the polymer backbone). If the epoxide is butylene oxide, then R' will be H and R" will be ethyl (or vice versa).

It will also be appreciated that if a mixture of epoxides are used, then each occurrence of R' and/or R" may be different, for example if a mixture of ethylene oxide and propylene oxide are used, R' may be independently hydrogen or methyl, and R" may be independently hydrogen or methyl.

Thus, R' and R" may independently be selected from hydrogen or alkyl, or R' and R" may together form a cyclohexyl ring, preferably R' and R" may independently be selected from hydrogen, methyl or ethyl, or R' and R" may together form a cyclohexyl ring.

W corresponds to W described above, except that a bond replaces the labile hydrogen atom. Therefore, the identity of each W depends on the definition of W in the chain transfer agent.

The variable a will also depend on the nature of the chain transfer agent. It will be appreciated that the value of a in formula (IV) will be the same as in formula (III). Therefore, for formula (IV), a is an integer of at least 2, preferably a is in the range of between 2 and 8, preferably a is in the range of between 2 and 6.

The value of a will influence the shape of the polyether carbonate polyol product. For example, when a is 2, the polyol of formula (IV) may have the following structure:

wherein Z, W, m, n, R' and R" are as described above for formula (IV).

For example, when a is 3, the polyether carbonate polyol of formula (IV) may have the following formula:

Where Z, W, m, n, R' and R" are as described above for formula (IV).

The polymer products may have any suitable number-average molecular weight (Mn). Preferably, the number-average molecular weight (M_n) of the polymer products may be from about 1 ,000 g/mol to about 100,000 g/mol. The number-average molecular weight (Mn) of the polymer products may be measured by Gel Permeation Chromatography (GPC) using, for example, a GPC-60 manufactured by Polymer Labs, using THF as the eluent at a flow rate of 1 ml/min on Mixed B columns, manufactured by Polymer Labs. Narrow molecular weight polystyrene standards can be used to calibrate the instrument.

The chain transfer agent may be used to control the molecular weight (M_n) of the polymer products. For example, it is possible to produce polyether carbonate polyols and polyester polyols having a M_n of from about 200 g/mol to about 20,000 g/mol, preferably less than about 10,000 g/mol by adding a chain transfer agent to the polymerisation process.

The polymer products may have a polydispersity index (PDI) of less than about 2, preferably less than about 1 .5, even more preferably less than about 1 .2. Advantageously, it is possible to control the molecular weight distribution so as to produce multi-modal or broad molecular weight distribution polymers by the addition of one or more chain transfer agent(s).

The polymer products are useful building blocks in the preparation of various copolymeric materials. The polymer products may undergo further reaction, for example to produce polymeric products such as polyureas or polyamines. These processes and reactions are well known to the skilled person (for example, refer to WO2013/034750).

The polyether carbonate polyols or polyester polyols may be used in various applications and products which conventionally use polyols, including (but not limited to) adhesives (such as hot melt adhesives and structural adhesives), a binder (such as forest product binders, foundry core binders and rubber crumb binders), coatings (such as powder coatings, transport, e.g. automotive or marine coatings, fast cure coatings, self-healing coatings, top coats and primers, varnishes, and coatings for marine applications, e.g. oil rigs), elastomers (such as cast elastomers, fibres/spandex elastomers, footwear elastomers, RIM/RRIM elastomers, synthetic leather elastomers, technical microcellular elastomers and TPU elastomers), flexible foams (such as viscoelastic foams), rigid foams (such as rigid and flexible panels, moulded rigid foams, aerosol gap filling foam, spray foams, refrigeration foams, pour-in-place foams, and foam slabs) and sealants (such as glazing sealants for commercial, industrial and transport (e.g. automotive) applications, and construction sealants). The polyamines and polyureas can be processed using methods standard techniques known in the art, such as foaming. It will be understood that the polyether carbonate polyol and polyester polyols produced by the polymerisation process of the first and third aspects of the present invention, or of the polymer of the fourth aspect of the present invention, may be mixed with other polyols prior to further use or reaction.

The polyether carbonate polyols may have a number of beneficial properties including high strength, high toughness, high gloss, high transparency, low haze, high gas (e.g. oxygen and carbon dioxide) or water barrier properties, flame resistance, UV resistance, high durability, rigidity and stiffness, compatibility with plasticizers, broad dimensional stability temperature, biodegradability and biocompatibility, and modulus of elasticity and yield strength comparable to LDPE. Thus, these polymers may be used in various applications and products, such as electronic components, construction materials, data storage products, automotive and aircraft products, security components, medical applications, mobile phones, packaging (including bottles), optical applications (such as safety glass, windscreens, etc).

All of the features contained herein may be combined with any of the above aspects and in any combination. Embodiments of the invention will now be described with reference to the following non-limiting examples.

Examples

Example 1 : Synthesis of catalysts 1 -3

L1 1 = M = Co

2 = M = Zn

3 = M = Ni

Catalysts 1 -3 were prepared according to the procedures described in Li et al, Acta Cryst, 2010, p726 and Li et al, Polym. Chem., 2014, p 4875 with the exception that 2,2-dimethyl-1 ,3- propanediamine and 2-(2-hydroxy-5-methylphenyl)benzotriazole were used as starting materials xample 2: Synthesis of catalysts 4 & 5

M = Co

M = Ni

L2 was synthesised from L1 by the following method: L1 (1 g, 1 .75 mmol), was mixed with MeOH (50 ml_) and stirred. Then, NaBH₄ (10 eq., 0.66 g, 17.5 mmol) was added portion-wise to the mixture over 30 mins. The mixture was stirred at room temperature for 2 hours after which water (150 ml_) was added to precipitate the product. The product was isolated by filtration, washed with water, dissolved in DCM and dried with Na₂S0₄ to give the product as a yellow solid 70 %, 0.7 g. H NMR (500 MHz, Chloroform-d) δ 7.88 - 7.82, 7.75, 7.39-7.32, 6.93, 3.85, 2.46, 2.24, 0.86.

Catalyst 4: L2 (0.350 g, 0.61 mmol) and Ni(OAc)₂.4H₂0 (0.302 g, 1 .21 mmol) were mixed with EtOH (15 ml_) and heated to reflex overnight. The resulting green precipitate was isolated by filtration and washed with pentane to give the bis-Ni complex (61 %, 0.30 g).

MS(ES): m/z = 749 [100 %, (M - OAc)⁺]

Catalyst 5: L2 (0.350 g, 0.61 mmol) and Co(OAc)₂.4H₂0 (0.303 g, 1 .21 mmol) were mixed with EtOH (15 ml_) and heated to reflex overnight. The brown solution had the solvent removed by rotary evaporation, the solid redissolved in DCM, filtered and the solvent removed to give the desired product as a dark brown solid (71 %, 0.35 g).

MS(ES): m/z = 810 [20 %, (M - OAc) ], 750 [100 %, M -OAc-2H] Example 3: Synthesis of catalysts 6 & 7

L4 and catalyst 7 were made according to Lin et al., ChemCatChem, 2016, 8, 984.

L3 was made via the same procedure using 2-(2-hydroxy-5-methylphenyl)benzotriazole as follows: a mixture of 2-(2-hydroxy-5-methylphenyl)benzotriazole (5 g, 22.2 mmol), Ν,Ν'- dimethylethylenediamine (0.978 g, 1 1 .1 mmol), para-formaldehyde (0.669 g, 22.2 mmol) in EtOH (6 ml_) was refluxed at 80 °C for 3 days. The mixture was cooled, extracted into DCM, washed with brine, dried over MgS0₄ and the solvent removed. L3 was recrystalised from a DCM/MeOH mixture to give the clean product in 55 % yield. H NMR (500 MHz, Chloroform-d) δ 7.87, 7.68, 7.36, 6.98, 3.68, 2.67, 2.24, 2.22.

MS(ES): m/z = 563 [100 %, (M+H)⁺]

Catalyst 6: L3 (1 g, 1 .8 mmol) was mixed with Ni(OAc)₂.4H₂0 (0.997 g, 3.6 mmol) in methanol (12 ml_) and refluxed for 3 days. The mixture was then cooled, solids isolated by filtration and washed with hexanes to give the desired product in 65 % yield.

MS(ES): m/z = 735 [100 %, (M - OAc)⁺]

Example 4: Synthesis of catalysts 10 & 11

Compound 8 was synthesised according to Song et al, J. Org. Chem., 2012, 77, 4759. Compound 9 was synthesised according to DiMauro et al., J. Am. Chem. Soc, 2002, 124(43), 12668

L5 Y = piperidine 10 = Z = piperidine

L6 Y = NMe₂ 11 = Z = NMe₂

L5: Compound 8 (0.835 g, 3.03 mmol) and 2,2-dimethyl-1 ,3-propanediamine (0.155 g, 1 .52 mmol) were mixed in MeOH (50 ml_) overnight at room temperature after which solvent was removed to give the diimine product. The diimine was taken to the next step without further purification. To a solution of the diimine compound (1 .44 g, 5.23 mmol) in MeOH (50 ml_) was added portion-wise NaBH₄ (1 .9 g, 52.3 mmol, 10 eq). The mixture was stirred at room temperature for 1 our then diluted with NaHC0₃. The product was extracted with ether, washed with brine, dried over Na₂S0₄ and the solvent removed to give the product as a light brown oil. H NMR (400 MHz, Chloroform-d) δ 7.12, 6.93, 3.82, 3.64, 2.56 - 2.44, 1 .63, 1 .50, 1 .29 (s, 18H, *Bu), 0.96.

MS(ES): m/z = 621 [100 %, (M+H)+] L6: was prepared using the same procedure for L5, starting from compound 9. H NMR (400 MHz, Chloroform-d) δ 8.38, 7.39, 7.20, 3.55, 3.50, 2.32, 1 .34, 1 .09.

Catalyst 10: A mixture of L5 (0.4 g, 0.8 mmol, 1 eq) and Ni(OAc)₂.4H₂0 (0.32 g, 1 .6 mmol, 2 eq) were suspended in MeOH and stirred for 4 hours after which solvent was removed, and then the residue re-dissolved in diethyl ether and filtered. The resulting green solution had the solvent removed, was re-dissolved in pentane then solvent removed again to afford a light green solid (0.38 g, 4.4 mmol, 69 %). MS(ES): m/z = 779 [20 %, (M - 20Ac + formate)⁺], 793 [100 %, (M - OAc)⁺]

Catalyst 1 1 : A mixture of L6 (1 .00 g, 1 .85 mmol), and Ni(OAc)₂.4H₂0 (0.530 g, 3.70 mmol) was stirred in MeOH (100 ml_) for 3 hours after which solvent was removed. The product was extracted into a mixture of DCM (5 ml_) and ether (20 ml_) and filtered. Solvent removal gave the desired compound 94 % yield.

MS(ES): m/z = 701 .22 [50 %, (M - 20Ac + formate)⁺], 597.51 [100 %, (M - OAc)⁺]

Example 5: Synthesis of catalysts 12-15

12 = amine 14 = amine

13 = imine 15 = imine

The ligands used in making catalysts 12-15 were synthesised according to Thevenon et al, Inorg. Chem., 2015, 54, 1 1906. Catalysts 12-15 were synthesised using the same methods except using 2 equivalents of Ni(OAc)₂.4H₂0.

Example 6: Synthesis of catalysts 16 & 17

L7 = 2,2-dimethylpropanediyl 16 = 2,2-dimethylpropanediyl

L8 \ = cyclohexanediyl 17 \ = cyclohexanediyl

L7: L7 was synthesised by methylating the ligand used in the synthesis of catalyst 14 according to the following procedure: Ligand (0.5 g, 1 .30 mmol) was mixed with acetic acid (4.3 mL) and acetonitrile (20 mL). To this was added formaldehyde (37 % in water, 1 mL) and the reaction stirred for 30 mins after which NaBH₄ (0.25 g, 6.5 mmol) was added and the reaction stirred at room temperature overnight. Solvent was removed and the residue hydrolysed with 2 M NaOH until pH 7 and extracted with DCM. After drying with Na₂S0₄, the mixture was filtered and solvent removed to give the crude di-methylated ligand as an off-white solid 75 % yield. Recrystallisation from hot EtOAc gives the product as a white microcrystalline solid. H NMR (500 MHz, Chloroform-d) δ 6.83, 6.74, 6.68, 3.87-3.8, 3.73, 2.77 - 2.72, 2.30, 2.06 - 2.00, 1 .85 - 1 .78, 1 .28, 1 .20 - 1 .12.

L8: L8 was synthesised by methylating the ligand used in the synthesis of catalyst 12 (1 g, 2.67 mmol), which was dissolved in a mixture of THF (3 mL) and acetonitrile (9 mL) and Na₂C0₃ (0.708 g, 6.75 mmol). To this was added dimethylsulfate (0.68 g, 0.51 mL, 5.4 mmol) and the reaction stirred overnight at room temperature. The crude product was purification by column chromatography, 50 % yield. H NMR (500 MHz, Chloroform-d) δ 6.83, 6.76, 6.60, 3.91 , 2.56, 2.34, 1 .45, 1 .12.

ESMS: m/z = 403 [100 %, (M+H)⁺]

16/17: Catalysts 16 & 17 were synthesised by mixing the ligands (1 .2 mmol) with and Ni(OAc)₂,4H₂0 (0.60 g, 2.41 mmol) in MeOH overnight (50 mL). Solvents were then removed giving the target complexes as a green solids.

17: MS(ES): m/z = 575 [100 %, (M-OAc) ]

Example 7: Synthesis of catalyst 18

The synthesis of L9 is described in WO2016012785.

18: To a suspension of half-macrocycle dialdehyde above (300 mg, 1 .0 eq) in DCM (15 mL) and MeOH (15 mL) was added Ni(OAc)₂.4H₂0 (300 mg, 2.2 eq). The resulting suspension was then stirred 3h at RT. Water (25 mL) was added, and the biphasic mixture was stirred vigorously for 10 min. Phases were separated, aqueous phase was extracted with DCM (10mL) and MeOH (10 mL) was added to the organic phase. The organic phase was dried over Na₂S0₄, filtered, and dried in vacuo. This yielded the desired product (343 mg, 80%). MS(ES): m/z = 655.2 [M-OAc] xample 8: Synthesis of catalysts 19 & 20

L10 L11 19 20

L10 was synthesised by reaction of L9 (1 g, 1 .0 eq) in EtOH (50 mL) with added AcOH (0.23 mL, 2.0 eq). The resulting mixture was then stirred for 20 min at 50°C. After this time, iso- butylamine (0.4 mL, 2.0 eq) and Na₂S0₄ (1 .42 g, 5 eq) were added, and reaction mixture was refluxed for 2 h. After this time, reaction was allowed to cool to RT and reaction mixture was filtered. A yellow precipitate formed and was discarded. The mother liquor was evaporated to give the crude product in 60 % yield.

MS(ES): m/z = 593.4 [M+H]⁺

L1 1 was synthesised by reduction of L10 (1 g, 1 eq), which was dissolved in MeOH (50 mL) and NaBH₄ (168 mg, 2.65 eq) added. Reaction mixture was stirred for 16 hours at room temperature. Solvents were evaporated in vacuo, and residue was dissolved in a mixture of DCM and water. The organic phase was extracted with DCM and dried over Na₂S0₄. Solvents were evaporated in vacuo to yield the clean product (316 mg, 27%). H NMR (400 MHz, CDCI3) δ 7.02-6.99, 3.85, 2.50, 2.47, 1 .80, 1 .27, 0.96-0.90.

MS(ES): m/z = 597.5 [100 %, (M+H)]⁺.

19: To a mixture L10 (373 mg, 1 eq) in DCM (10 mL) and MeOH (10 mL) was added Ni(OAc)₂.4H₂0 (340 mg, 2.2 eq). The resulting mixture was then stirred ON at RT. Water (20 mL) was added, and the biphasic mixture was stirred vigorously for 10 min. Phases were separated, aqueous phase was extracted with DCM (10mL) and MeOH (10 mL) was added to the organic phase. The organic phase was dried over Na₂S0₄, filtered, and dried in vacuo. MS(ES): m/z = 765.2 [100 %, (M-OAc)]⁺

20: To a solution of L1 1 (275 mg, 1 .0 eq) in DCM (15 mL) and MeOH (15 mL) was added Ni(OAc)₂.4H₂0 (248 mg, 2.2 eq). The resulting suspension was then stirred for 3 h at RT. After this time, all solids went into solution. The solvent was removed in vacuo, this yielded the desired product (182 mg, 48%).

MS(ES): m/z = 769.2 [100 %, (M-OAc)]⁺.

Further Preparative Examples

21

Syni esss of 21

Into a 250mL flask, p-formaldehyde (4g), H₂SG₄ (0.4mL) and Hydrobromic acid were added under a nitrogen How at 70 "C. 2'-Hydroxy-4'-methylacetophenone (10g) was added and the reaction left overnight at 70°C after which the reaction mixture was cooled to room temperature. A red solid collected at the bottom of the flask. Et-,_:0 (50mL) was added and the organic phase coiiected, foiiowed by washing the aqueous phase with more Et₂0. The organics were combined and dried with Na₂S0₄. The Et₂0 was removed under vacuum. The soiid was recrystaiiised from petroleum ether: 9.74g (86.4%).

^!H NMR (§00 MHz, ChIoroform~d) δ: 12.61 , 7.49, 7.37, 4.55, 2.61 , 2.30.

22

Synthesis of 22

into a 100ml flask, Compound 21 (1g) was dissolved in 10 ml THF. N, N'-DimethyM ,3- propanediamine (0.27mL) in THF (0.73mL) was added over 2 hrs. Hunig's base (0.75 mL) was added over SOmins. The solution was left stirring overnight. The THF was removed from the reaction mixture and the residue extracted with DC . (0.9g).

'H NMR (S00 MHz, ChIoroform~d) δ: 7.44, 7.24, 3.56, 2.62, 2.49, 2.27, 2.25, 1.85-1.79. General Procedure A

Into a 100ml flask, 22 (0.44g) was dissolved n EtOH (20mL). Na₂S0₄ (1 45g) was added to the solution. The desired amine was then added to the solution. This was left overnight. The reaction mixture was filtered to remove the N¾S0₄ EtOH was removed under reduced pressure. The crude product was dissolved in DCM/Water and the organies extracted. The combined DCM iayers were dried with Na₂S0 before removing the DCM under reduced pressure.

23a

Benzyiamme 23a

Genera! Procedure A. Using benzyiamine (0.23mL) as the desired amine. The product was collected as a yeliow viscous oil (0.81 g, 97.3%).

¹H NMR (500 MHz, Chloroform-d) δ: 7.35, 7.34, 7.25-7.29, 7.25, 7.22, 4.77, 3.54, 2.45-2.48,

2.45, 2.27, 2.24, MS (ES+): m/z: 605.4.

23b

Ethy!amme 23b

General Procedure A. Using eihyiamine (5mL, 2M in THF) as [he desired amine.

^!H NMR (500 MHz, Chloroform-d) δ: 7,21 , 7.20, 3.58, 3.54-3.58, 2.49-2.55, 2.32, 2.28, 2.26, 1 .83-1 .89, 1 .34-1 .37. MS (ES }_: m/z: 481 .4.

23c isobutyiamine 23c

General procedure A. Using isobutylamine (0.4mL) as the desired amine,

¹H UMR (600 MHz, Chloroform-d) δ: 7.21 , 7.20, 3,56, 3.35, 2.47-2.50, 2.31 , 2.26, 2.00-2.08, 1 .81 -1 ,87, 1 .03-1 ,02, MS (ES+): m/z: 537.4,

General Procedure 8

In a 100mL R8F, imine was dissolved in eOH (20mL). NaBH (0.15g) was added to the solution . The MeOH was removed under vacuum and the solids dissolved in DC Water. The organios were extracted with DCM. The organic layers were combined and dried with Na₂S0₄. The DCM was removed under vacuum to afford the off white solid product.

24a

Synthesis of 24a

General Procedure B, Starting with 23a (Q.6g). The final yield of product was 0.47g (77.5%) ¹ H UMR (500 MHz, Chloroform-d) δ: 7.30, 7.29, 7.21 -7.25, 6.92, 6.75, 4.02-4.08, 3.64-3.70, 3.60, 2.48, 2.26, 2.24, 1 .79-1 .85, 1 .40-1 .41 . MS (ES+): m/z; 809.4.

24b

Syn es s of 24b

Genera! Procedure B. Starting with 23b (0.5g). The final yield of product was 0.44g {87,3%}.

¹H NWfR (500 MHz, Chloroform-d) δ: 6.85, 6.76, 4.01 , 3.60, 2.55-2,85, 2.48, 2.26, 2.22, 1 .81 , 1 .43, 1 .12. MS (ES+): m/z: 485.4.

24c

Synthesis of 24c

General Procedure B. Starting with 23c (0.44g) The final yield of product was 0.44g (89.6%).

¹H R (500 MHz, Chloroform-^) δ: 8,83, 6.78, 3,89-3.94, 3.57, 2.37-2.48, 2.24, 2,22, 1 .18, 1 .75, 1 .38, 0.89. MS (ES+): m/z: 541 .4.

General Procedure C

Into a 100mL RBF, iigand was dissolved in 5mL DC and 5mL eOH. Nickel acetate was added and the solution stirred overnight. The solvent was removed under vacuum.

25a Synthesis of 2Sa

Genera! Procedure C, Starting with 24a (0.44g) and nickel acetate (0.58g). Product was obtained as an emeraid green powder (0.41 g, 63.2%).

MS (ES+): m/z: 7812.

25b

Synthesis of 2Sh

General Procedure C. Starting with 24b (0.41g) and nickel acetate (0.41 g). The reaction was heated to 40°C. The product was obtained as an emeraid green powder (0.28g, 47.1%).

MS (ES+): m/z: 657.2.

25c

is of 25c

General Procedure C. Starting with 24c (O.SOg) and nickel acetate (O.Sg). The product was obtained as an emeraid green powder (0.54g, 85.7%).

26 Synthesis of 28

Into a 100ml flask, 21 (1g) was dissolved in THF (10mL). To this solution trans-N.N - dimethyicyciohexane-1 ,2-diamine (0.32mL) in THF (0.68mL) was added dropwise over 2hrs. Hunig's base (0.75mL) was added dropwise over 30mins. The solution was filtered and the precipitate washed with THF. The THF was removed from the filtrate and he solids was dissolved in DC /Water. The mixture was separated and the aqueous washed with a further DCM portions. The DCM layers were combined and dried with Na₂SQ₄ before being filtered into an RBF. The DCM was removed under vacuum leaving the desired product as a light yellow solid (Q.97g).

MS (ES+): m/z: 467.3.

27a

Synthesis of 27a

into a 100mL flask, 26 (0.45g) was dissolved in EtOH (20mL) and Na₂S0₄ (0.75g) was added to the reaction mixture, isobuty!amine (0.21 mL) was added to the solution which was then left overnight. The EtOH was removed and the solids that remained were dissolved in DCM/Water.

The organics were extracted into the DCM and the layers separated . The DCM layers were combined and dried with Na₂S0 . The DCM was then removed under reduced pressure to leave the product as a yellow solid (0.52g, 93.8%)

MS (ES+): m/z: 577.4.

27b

Synthesis of 27b

into a 100mL flask, 26 (0.45g) was dissolved in EtOH (20mL) and Na₂S0₄ (0.75g) was added to the reaction mixture. 2M Ethylamine solution in THF (2.7mL) was added to the solution before leaving overnight. The solution was filtered and then reduced under vacuum to give a yellow solid (Q.52g, 93%)

MS (ES+): mfe: 521 .4.

28a

Synthesis of 28a

Into a l OOmL flask, 27a (Q.52g) was dissolved in MeOH (10mL). NaBH₄ (0.27g) was added in a few portions to the reaction mixture. Once complete, the MeOH was then removed under reduced pressure before dissolving the soiids in DC Water. The organics were extracted into the DCM layer and separated in a separatory funnel. The DCM layers were combined and dried over Na₂S0₄ before filtering . The DCM was removed to give the final product as an off- white powder (0.48g, 91 .0%).

MS ;ES÷ =: rn/z: 581 .5.

28b

Synthesis of 28b

Into a 100ml flask, 27b (0.52g) was dissolved in MeOH (20mL). To this NaBH* (0.29g) was added in portions over 10 mins. The reaction mixture was left overnight. The solution was reduced under vacuum before the solids were dissolved in DCM/Water. The organics were extracted into DCM and the aqueous layer washed with DCM. The organic layers were combined and dried with Ma₂SO,¾. The DCM was removed under vacuum to give an off white solid.

MB (ES+): m/z: 525.4.

29a

Synthesis of 29a

Into a l OQmL flask, 28a (0.48g) was dissolved in DCM (5mL) and eOH (5mL). Nickel acetate (0.32g) was added and the solution stirred overnight. The solvent was removed under vacuum. (0.54g, 84.0%).

MS (ES+): mfe: 753.2.

29b

Synthesis of 29b

Into a 100ml RBF, 28b (Q.57g) was dissolved in MeOH (5ml) and DCM (5mL). Nickel acetate (0.54g) was added and the solution stirred overnight. The solvent was removed under vacuum affording a dark green powder (0.60g, 70.4%)

MS (ES+): m/z: 697.2

General Procedure D

Into a 100ml RBF, ¾ macrocycie dialdehyde was dissolved into 10ml of EtOH. Na₂S0₄ was added Into the flask. The reaction mixture was stirred to suspend it in the solution . The amine was then added in one portion. The reaction mixture was left stirring vigorously overnight. (~16hrs). Once the reaction was complete the solution was filtered through a cotton plug before removing the EtOH on a rotary evaporator to give the solid product.

30a

Synthesis of 30a

General Procedure D. ¾ macrocycle diaidehyde 40 (0.9g) was used in this reaction. The amine used was isopropyl amine (0.43mL). Once compiete the solvents were removed to afford the product.

¹H N fS O MHz, Chloroform-d) δ; 8.44, 7.43, 7,26, 3.52, 2.69, 2.27, 2.03, 1 ,76, 1 .26 - 1.25, 1 .24. MS (ES+): m/z: 605.4.

30b

Synthesis of 30b General Procedure D. ¾ macrocycle diaidehyde (0.9g) was used in this reaction. The amine used was t-butyiamine (0.54mL). A further portion of t-butyi amine (0.15mL) and a₂S0₄ (0.5g) was added after the first day with another 24hrs reaction time. Solvent was removed to leave solid product (93.8%).

¹H NMR (500 MHz, Chloroform-d) δ: 8.37, 7.53, 7.18, 2.71 , 2.31 , 2.02, 1.74, 1.31 , 1 ,27, 1 .26 - 1 ,12. MS {ES+y, m/z: 633,5.

31

Synthesis of 31

Reaction was completed under an Inert atmosphere. A sample of 30a (200mg) was dried in a Schienk f!ask for one hour under high vacuum. To the dried powder anhydrous nickel acetate (0.13g) was added and dissolved in dry MeOH (10ml). The methanol was then removed in vacuo.

MS (ES÷): m/z: 783.2.

Ge eral Procedure E

Into a 100mL RBF, 22 was diluted with EtOH (10mL). To this solution NaBH₄ was added over 1 Smins. The reaction mixture was left for 2hrs. EtOH was removed and the solids were dissolved in DCM/water. The mixture was transferred to a separatory funnel and the DCM was removed. The aqueous layer was washed with DCM. The DCM layers were combined and dried with a brine wash and then Na₂S0₄. This solution was then filtered through a cotton plug and he DCM was removed under vacuum before further drying on a Schienk line overnight. This afforded the solid product.

32a

Synthesis of 32a Genera! Procedure E, Using 30a (0.5g) and NaBH (60mg) was used to reduce the sample. Off white solid was collected.

¹H NMR (500 MHz, Chloroform-d) δ: 7.01 , 3.79, 3.62, 2.81 , 2.65, 2.21 , 2.02, 1.77, 1 .21 , 1 .17 - 1 .09, 1 .06. MS (ES-i-): m/z: 609.5.

3^2b

Sy eses of 32b

General Procedure E. Using 30b (0.5g) and NaBH₄ (60mg) was used to reduce the sample.

Off white solid collected.

¹H NMR (500 MHz, Chioroform-d) 7.03, 3.73, 3.59, 2.65, 2,21 , 2.02, 176, 1 .20, 1 .14. MS (ES+): m/z: 637.5.

33

Synthesis of 33 p-formaidehyde (5.6g), HBr (50mL) and H₂S0₄ (0.8mL) were combined and purged under N₂. 4-tert-butyl-2-formylphenoi (1 1 g) was added to the solution, heated to 70 oC and stirred overnight. Solution cooled to room temperature and washed with Et_zO/H₂0, washing the aqueous layer with Et₂0. The Et₂0 layers were combined and dried with a brine wash and then Na₂S0₄, filtered, and the soivent removed. 10.5g (65.8%).

¹H NMR (500 MHz, Chioroform-d) δ: 11.32, 9.89, 7.64, 7.51 , 4.59, 1.33. MS (ES+): m/z: 191 .1 .

34

Syn e s of 34

Into a 250mL RBF, 33 (0.5g) was dissolved in THF (40mL). A solution of N,N-dimethyM ,2- diaminocyciohexane (0.1 ml) in THF (10ml) was added to the solution over 30min. Et₃N (0.26mL) was added. The reaction mixture was left overnight (16hrs). Reaction was filtered.

The soiuiion was reduced to dryness on a rotar evaporator. This gave the product as a brown solid.

¹H N R (500 MHz, Chloroform-d) δ: 11.18, 9.97, 7.42, 7.31 , 7.05 - 6.97, 4.36, 2.74, 1.15. MS (ES+): m/z: 517.3.

35

Synthesis of 3S

into a l OQmL RBF, 34 (0.47g) was dissolved in BOH (25mL). Na₂S0₄ (0.5g) was added to the solution, Ethylamine (1.4mL. 2 in THF) was added. The reaction mixture was left overnight (16hrs). Once compiete, the solvents were removed en the rotary evaporator. The remaining solids were dissolved in DCM/Water. The product was extracted into the DCM layer which was washed with brine before drying with Na₂S0₄. The DCM was removed to give the product, as a light brown solid with a yield of 0.52g (99.1 %)

*H NMR (500 MHz, Chloroform-d) δ: 8.34, 7.17, 7.06, 6.98 - 6.95, 6,92 - 6.88, 4.55, 3,61 , 2.82, 1 ,30, 1 , 10. MS (ES+): m/z: 571 ,4.

Synthesis of 38

Under anhydrous conditions, Ligand 35 (330 mg) and Ni{OAc)₂ (203 mg) were dissolved in MeOH (8 ml) and left to stir at room temperature overnight. The methanol was then removed

\n vacuo.

MS (ES+): m/z: 743.2, 729.2,

Genera! Procedure F

To a solution of 5-(fe/f-butyl)-3-(1 ,3-dioxan-2-yi)-2-hydroxybenzaidehyde in ethanoi was added magnesium sulfate and desired diamine. The reaction mixture was stirred at room temperature for 3 h^■■■■ 19 h then filtered. The filter cake was washed with DCM and concentrated to dryness in vacuo to afford the desired product.

37a

Synthesis of 37a

General Procedure F. 5-(ferf-butyi)-3-(1 ,3-dioxan-2-yl)-2-hydroxyben∑aidehyde (10.4 g), ethanoi (350 ml_), anhydrous magnesium sulfate (23.7 g) and 2,2-dimethyipropane-1 ,3- diamine (2.36 ml), the title compound was obtained as a yellow powder (11.4 g, 97%).

¹H NMR (500 MHz, Chloroform-d,) δ: 13.77, 8.32, 7.71 , 7.24, 5.96, 4.33 ~ 4.26, 4.12 - 4.06, 3.46, 2.26 - 2.36, 1 .50 - 1 .42, 1 .31 , 1 .07. MS iES-i--: m/z: 595, m/z: 617,

37b

Synthesis of 37b

General Procedure F, 5-(fe f-butyi)-3-(1 ,3-dioxan-2-yl)-2-hydroxybenzaidehyd8 (5.50 g), ethanoi (150 mL), anhydrous magnesium sulfate (1 1 .4 g) and f/ans-1 ,2-diaminocyciohexane ( .22 mL), the title compound was obtained as a yellow powder (5.96 g, 52%).

'H NMR (500 MHz, Chioroform-d) 6: 13.73, 8.23, 7.60, 7.12, 5.85, 4.29 - 4.25, 4.06 - 4.00, 3.28 - 3.20, 2.29 - 2.17, 1 .91 - 1 .79, 1 .47 - 1.41 , 1 .2. MS (ES+): m/z: 807, m/z: 829.

Genera! Procedure G

A solution of imine-protected aldehyde in methanol was cooled to 0 "C, then sodium borohydnde was added portion wise. The reaction mixture was left to stir and warm to room temperature for 5 h - 19 h. The methanol was removed in vacuo then water was added. The onganics were extracted with dichioromethane, dried over anhydrous sodium sulfate, filtered and concentrated to dryness in vacuo to afford the desired product.

38a Synthesis of 38a

Genera! Procedure G. 37a (1 1 A g), methanol (100 mL), tetrahydrofuran (100 ml) and sodium borohydnde (33.2 g), the titie compound was obtained as a pale yellow powder (9.83 g, 86%).

^!H UMR (SO MHz, Chioroform-d) δ; 7.47, 7,00, 5.85, 4.28 - 4.24, 4.05 -- 3.99, 3.93, 2.50, 2.31 - 2.19, 1 .43 - 1 .40, 1 .28, 0.97, MS |ES÷): m/z: 599,

38b

Synthesis of 38b

General Procedure G. 37b (5.67 g), methanol (150 ml) and sodium boroyhydride (3.53 g), the titie compound was obtained as a cream powde (5.1 1 g, 90%).

'H NMR fSQQ MHz, Ch!oroform~d) δ: 7.41 , 7.05, 5.82, 4.33 - 4.25, 4.08 - 4.0, 3.83, 2.43 -

2.37, 2.28, 2.18, 1.73, 1 .46, 1.30, 1.27 - 1.16.

General Procedure H

To a solution οί^' amine-protected aldehyde in tetrahydrofuran was added 1 hydrochloric acid solution. The reaction mixture was stirred and refluxed overnight. The tetrahydrofuran was removed in vacuo then the organics were extracted with dichioromethane, dried over anhydrous sodium sulfate, filtered and concentrated to dryness in vacuo.

39a

Synthesis of 33a

General Procedure H. 38a (9.83 g), tetrahydrofuran (100 ml) and aqueous hydrochloric acid solution (400 ml), the title compound was obtained as a white powder (4.83 g, 53%).

^!H NMR (500 MHz, Chioroform-d) δ: 10.00, 7.99, 7,89, 7.51 , 7.41 - 7.38, 5.62 - 5.59, 5.50, 4.39, 4.32, 3.15, 3.08, 138, 131 , 121 , 119. LCSVIS (ES^÷) 1 .53 min, m/z: 483.

39b

Synthesis of 39b

Genera! Procedure H, 38b (5.1 1 g), tetrahydrofuran (100 ml) and aqueous hydrochloric acid soiuiion (200 ml), the title compound was obtained as a white powder (2,94 g, 62%).

*H UMR (600 MHz, Chioroform-d) δ: 1 1 .33, 10.41 , 10.2, 9.88, 8.22, 7.54, 4.25, 4.10, 3.92, 2.40 - 2.35, 1 .88 - 1 .79, 1 .30. MS {ES*): m/z: 495.

40

Sym¾esss of 40

To a solution of 3-(bromomethyi)-5-(fert-butyl)-2-hydroxyb8nzaidehyde (5.00 g) in tetrahydrofuran (40 ml) was added a solution of frans-M/V-Dimethyicyciohexane-1 ,2-diamin8

(2.9 ml) in tetrahydrofuran (20 ml), followed by triethyiamine (3.2 ml). The reaction mixture was left to stir at room temperature overnight. The reaction mixture was then concentrated to dryness in vacuo, water was added, and the organics were extracted with dichioromethane, dried over anhydrous sodium sulfate, filtered and concentrated to dryness in vacuo to afford a yellow powder (4.71 g, 98%).

¹H UMR (500 MHz, Methanol-d4) δ: 10.06, 7.61 , 7.53, 3.83, 2.96, 2,30, 2.20 - 2.12, 1 ,90 ^■■■■ 1 ,84, 1 .44 - 1 .33, 1 .32 - 1 .24, 1 .22. MS (ES⁺): rn/ : 523. NH OLi O

41

Synthesis of 41

To a solution of 39a (4.67 g) in methanol (140 mL) was added lithium hydroxide (0.89 g). The reaction mixture was left to stir at room temperature overnight. The reaction mixture was then filtered to afford a yei!ow powder (2.55 g, 61 %),

¹H NM (500 MHz, Chloroform-d) δ: 9.56, 7.29, 7.25, 3.56, 2.56, 1 .28, 0.97. MS (ES*): m/z:

483.

General Procedure \

To a solution of amine-aidehyde in ethanoi was added anhydrous sodium sulfate, followed by desired amine. The reaction mixture was left to stir at. room temperature overnight. The reaction mixture was then filtered and concentrated to dryness in vacuo to afford the desired product.

42a

Syn e s of 42a

General Procedure i. 39a (450 trig), ethanoi (10 mL), anhydrous sodium sulfate (575 mg) and benzyiamine (0.18 mL), the title compound was obtained as a yellow powder (473 mg, 88%).

¹H NMR (500 MHz, Methanol-d4) δ: 8.60, 7.47 -- 7.44, 7.32 -- 7.28, 4.80, 4.12, 2.93, 1.32, 1 .07. MS C£S^÷): m/z: 881 .

42b

Syrs esss of 42b

General Procedure I, 39a (450 mg), ethanoi (10 mL), anhydrous sodium sulfate (575 mg) and ethyiamine (2 In THF, 1 .0 mL), the title compound was obtained as a yellow powder (421 mg, 97%).

¹H UMR (500 MHz, Methanol-d4) δ: 8.44, 7.40, 7.34, 3.97, 3.66 ~ 3.56, 2.98, 2.84, 1 .29, 1 .03.

MS (ES⁺): m/z: 537.

42c

General Procedure i, 39a (200 mg), ethanoi (20 mL), anhydrous sodium sulfate (/1 Q mg) and Y-aminobutyric acid (106 mg), the title compound was obtained as a ye!low powder (196 mg,

H NMR (500 MHz, DMSO~d6) δ: 8.55, 7.42, 7.37, 3.87, 3.56 - 3.53, 2.70, 2.27 -- 2.23, 1 .23, 0.94. MS (ES⁺): m/z: 653, m/z: 596.

42d

Sy eses of 42 f

General Procedure I, 39a (200 mg), ethanoi (20 ml), anhydrous sodium sulfate (710 mg) and 2-(aminomethyi)phenol (127 mg), the title compound was obtained as a yellow powder (145 mg, 51 %).

¹H NMR (500 MHz, DMSO-dS) δ: 8.64, 7.39, 7.31 ~ 7.29, 7.22 ~ 7.19, 7.14 ~ 7.12, 7.09 ~ 7.05, 6.95^■■■■ 6.91 , 6.87^■■■■ 6.80, 6.72 -- 6.89, 4.89, 3.85, 2.70, 1.24, 0.93. MS <ES*): m/z: 693 .

43a

Synthesis of 43a To a solution of 42a (425 mg) in methanol (15 ml) was added sodium borohydride (51 mg, 2.1 eq). The ieaction mixture was stirred at room temperature overnight. The methanol was removed in vacuo then water was added. The organics were extracted with dichioromeiharse, dried over anhydrous sodium sulfate, filtered and concentrated to dryness in vacuo to afford a yellow powder (352 mg, 82%).

*H UMR (500 MHz, Chioroform-d) S; 7.33 - 7.31 , 7.02, 7.00, 3.87, 3,81 , 2,53, 1 .27, 0.96. MS (ES*): m/z: 885.

43b

Synthesis of 43b

To a solution of 42b (373 mg) in methanol (15 mL) was added sodium borohydride (55 mg, 1 ,5 mmoi, 2.1 eq). The reaction mixture was stirred at room temperature overnight. The methanol was removed in vacuo then water was added. The organics were extracted with dichioro methane, dried over anhydrous sodium sulfate, filtered and concentrated to dryness in vacuo to afford a yellow powder (378 mg, 85%).

'H NMR (500 MHz, Chioroform-d) 6: 7.02, 6.99, 3.85, 3.48, 2.70, 2.51 , 1.27, 1.14, 0.95. MS

44

General Procedure L Using 41 (1 g), ethanol (250 mL), anhydrous sodium sulfate (1 .44 g) and benzylamine (0.55 ml), the title compound precipitated after concentration of^" the filtered reaction mixture as a yellow powder (881 mg, 66%).

¹H NMR (500 MHz, Chloroform-d) δ: 8,14, 7.20 - 7.09, 4,44, 3.74 -- 3.69, 2.46, 1 .29, 0.93. MS (ES⁺): m/z: 661 .

45a

Synthesis of 4§a

General Procedure L Using 39b (200 mg), ethanoi (10 mL), anhydrous sodium sulfate (250 mg) and benzyiamine (0.10 mL), [he title compound was obtained as a yei!ow powder (207

H HMR (500 MHz, ethanol-d4) δ: 6.86, 5.77 - 5.70, 5.62 - 5.55. 3.06 - 3.01 , 2.37 - 2.31 , 2.23, 1 ,75 - 1 ,64, 0,94, 0,67 - 0.55, 0,16, -0.36. MS (ES*): m/z: 673.

45b

Synthesis of 4Sb General Procedure I. Using 39b (350 mg), ethanoi (25 mL), anhydrous sodium sulfate (438 mg) and y-aminobutyric acid (159 mg), the title compound was obtained as a yellow powder (239 mg, 59%),

¹H NMR (500 MHz, DMSO-dS) δ: 8.55, 7.48, 7.37, 4.02, 3.86, 2.64 ~ 2.62, 2.33, 2.24, 2.18 ~

2.14, 1 .81 - 1 .71 , 1 .23.

46a

Syn eses of 46a

General Procedure i. Using 40 (500 mg), ethano! (10 ml), anhydrous sodium sulfate (679 mg) and benzylamine (0.21 mL). the title compound was obtained as a yeiiow powder (386 mg,

58%),

*H M R (S00 MHz, Chioroform-d) 5: 8.57, 7.38 - 7.28, 4,80 - 4.77. 3.79 - 3.68, 2.89 - 2,63, 2.24, 2,05, 1 ,78, 1 ,33 - 1 ,28, 1 ,23. MS (ES*): mfe: 701 .

46b

Synthesis of 48b

General Procedure I. Using 40 (500 mg), ethanol (10 mL), anhydrous sodium sulfate (679 mg) and ethyiamine (1.2 mL), the title compound was obtained as a yeiiow powder (388 mg, 67%).

¹H NMR (S00 MHz, Methanol^) δ: 8.41 , 7.32, 7.18, 3.74 - 3.61 , 3,52 - 3.43, 2.31 - 2.18, 2.13 - 2.03, 1.77, 1 .24 - 1.18, 1.14 - 1.1 1 , 1.07. MS (ES*): m/z: 577.

46c

Syn e s of 4βε

General Procedure 1. Using 40 (500 mg), ethanoi (10 roL), anhydrous sodium sulfate (679 mg) and 2-(aminomethyl)phenoi (247 mg), the title compound was obtained as a yellow powder (535 mg, 76%).

'H NMR {SQO MHZ, Methanol-d4) δ: 8.43, 7.40 - 7.14, 7.11 - 6.88, 6.83 - 6.67, 6.58, 4.67,

4.59 - 4.47, 4.07 - 3.92, 3.83, 2.58, 2.33 - 2.31 , 2.25 - 2.12, 1 .96 - 1 .83, 1 .53 - 1 .19, 1 .13, MS (ES^÷); m/z.: 733.

47

Synthesis of 47

To a solution of 39a (200 mg) in ethanoi (25 mL) was added anhydrous sodium sulfate (290 mg) and aniline (0, 1 mL). The reaction mixture was stirred at room temperature overnight. Molecular sieves were added and another equivalent of aniline (0.04 mL) then the reaction mixture was left to stir at room temperature overnight. Solvent removed.

MS (ES*): m/z: 633.

General Procedure J

To a solution of desired !igand In methanol was added nickel(l!) acetate tetrahydrate. The reaction mixture was stirred at room temperature overnight. The methanol was then removed in vacuo and water was added. The organics were extracted with dichioromethane, dried over anhydrous sodium sulfate, and concentrated to dryness in vacuo. The remaining residue was dissolved in methanol then concentrated to dryness in vacuo to afford the desired product.

48a

Syni esss of^" 4S&

General Procedure J, Using 42a (768 mg), methanol (50 ml) and nickei(ll) acetate tetrahydrate (568 mg), the title compound was obtained as a green powder (789 mg, 77%).

MS (ES⁺): m/z: 833, m/z: 821.

48b

Synthesis of 48b General Procedure J. Using 42b (301 mg), methano! (10 mi_) and nicke!(il) acetate tetrahydrate (279 mg), the title compound was obtained as a green powder (121 mg, 28%).

MS (ES⁺): m/z.: 709, m/z: 695.

48c

Syn e es of 4Sc

General Procedure J, Using 42c (250 mg), methanol (10 mL) and nickel(l!) acetat tetrahydrate (191 mg), the title compound was obtained as a green powder (191 mg, 58%).

MS (ES*): m/z: 789, m/z: 787, m/z: 724.

48d Synthesis oi 4Sd

General Procedure J. Using 42d, methanol (10 mL) and nicke!(!i) acetate tetrahydrate (215 mg), the title compound was obtained as a green powder (86 mg. 21 %).

MS (ES⁺): rn/z: 885, rn/z: 851 , m/z: 806,

49a

Synthesis of 49a

Genera! Procedure J. Using 45a (207 mg), methane! (10 ml)

tetrahydrate (1 53 mg), the title compound was obtained as a green pows

MS (ES⁺): m/z: 845, rn/ : 786.

49b

Synthesis of 43b

Genera! Procedure i. Using 33b (350 mg) , eihanol (25 ml), anhydrous sodium sulfate (440 mg) and ethyiamine (0.77 mL), the imine compound was obtained as a yei!ow powder. Genera! Procedure J. Im!ne was dissoived in methanol (10 mL) with nicke!(! S) acetate tetrahydrate (238 mg), the title compound was obtained as a green powder (210 mg, 57%).

MS (ES*): m/z: 721 , rn/z: 709, m/z: 694.

49c

Synthe i of 49c

General Procedure J. Using 45b (239 mg), methanol (10 mL) and nickel(ll) acetate tetrahydrate (182 mg), the title compound was obtained as a green powder (134 mg. 41 %). MS (ES⁺): m/z: 777. m/z: 735, m/z: 692,

Synthesis of 49d

General Procedure 1. Using 39b (350 mg), ethano! (25 mL), anhydrous sodium sulfate (438 mg) and 2-(aminomethyl)phenol (190 mg), the title compound was obtained as a yellow powder. General Procedure J. Imine was dissolved in methanol (10 mL) with nickel(ll) acetate tetrahydrate (205 mg), the title compound was obtained as a green powder (146 mg, 38%).

MS (ES*): m/z: 819,

50a is of SOa

General Procedure J, Using 48a (386 mg), methanol (10 mL) and nicke!(i!) acetate tetrahydrate (274 mg), the title compound was obtained as a dark green powder (431 mg, 81 %),

MS (ES^*): m/z: 847,

Synthesis of SO

Under anhydrous conditions. Ligand 46b (223 mg) and Ni(OAc)₂ (212 mg) were dissolved in eOH (8 ml) and left to stir at room temperature overnight. The methanol was then removed in vacuo.

MS (ES+): m/z: 749.2, 735.2.

50c ss of

General Procedure J. Using 48c (535 mg.), methanol (10 ml) and nickei(H) acetate tetrahydrate (363 mg), the title compound was obtained as a dark green powder (804 mg, 86%).

MS (ES*): m/z: 847.

51a

Sy eses of 51

General Procedure J . Using 43a (352 mg), methanol (20 ml) and nickei(ll) acetate tetrahydrate (263 mg) the title compound was obtained as a green powder (180 mg. 38%).

MS (ES⁺): m/z: 837.

51b Synthesis of SI b

Genera! Procedure J. Using 43b (320 mg), methanol (20 mL), nickei(ii) acetate tetrahydrate

(320 mg) and sodium hydroxide (50 mg). the title compound was obtained as a green powder (171 mg, 37%),

General Procedure K

To a solution of desired iigand in methanol was added cobait(ii) acetate tetrahydrate. The reaction mixture was left to stir at room temperature overnight. The reaction mixture was then concentrated to dryness in vacuo to afford the desired product.

52a

Synthesis of S2a

Genera! Procedure K. Using 45a (584 mg), methanol (20 mL) and cobalt(H) acetate tetrahydrate (432 mg), the title compound was obtained as a very dark green/biack powder

(777 mg, 99%). MS (ES*): m/z: 847, m/z: 833.

52b

S nt es s of^" 52b Genera! Procedure K. Using imine intermediate in 49b (473 mg). methanoi (20 mL) and cobalt (II) acetate tetrahydrate (429 mg), the title compound was obtained as a very dark green/biack powder.

MS (ES*): m/z: 722. m/z: 695.

Synthesis of S3a

General Procedure K. Using 42c (239 mg), methanol (20 mL) and cobait(ii) acetate tetrahydrate (189 mg), the title compound was obtained as a very dark green/biack powder (253 mg, 78%).

MS {ES*}: m/z: 826.

53b

Syni esss of S3h

General Procedure . Using 42d (286 mg), methanoi (20 mL) and cobalt(ll) acetate tetrahydrate (206 mg), the title compound was obtained as a very dark green/biack powder (322 mg, 84%).

MS {ES'}; m z: 925.

54

Synthesis of §4

To a solution of 42a (584 mg) in methanol (20 ml) was added magnesium(ii) acetate ietrahydrate (379 mg). The reaction mixture was left to stir at room temperature overnight. The reaction mixture was concentrated in vacuo, then left in the fridge over the weekend . The precipitate was filtered off and the mother liquor was concentrated to dryness in vacuo to afford a ye!iow powder. (274 mg, 44%).

H NMR (500 MHz, Methanoi~d4) 6: 8,57, 7.48 - 7.42, 7,42, 7.34, 7,28^■■■■ 7.20, 7.18 - 7,14, 4.74, 3.85, 2,78, 1 ,30, 0,97.

55

S nt esis of SS

To a solution of 42b (473 mg) in methanol (20 ml) was added zinc(ii) acetate dihydrafe (387 mg). The reaction mixture was left to stir at room temperature overnight. The reaction mixture was then concentrated to dryness in vacuo to obtain the desired product as an orange red powder (609 mg, 76%).

MS (ES*): m/z: 721 , m/z: 893.

General synt es L The 2-formyl-4-ferf-butyi-6-bromomethylphenol was dissolved in THF and cooled to 0 °C. The diamine was dissolved in THF and added slowly. At the end of addition, triethyiamine was added dropwise, and the reaction was warmed to room temperature and left stirring for 2-18 hours,

At the end of the reaction THF was removed, DC was added and then the organics were washed 2x with aq, NaHC0₃ solution. The organics were dried over Na₂S0₄, the solvents were removed after filtration.

General synthesis L. 2-formyi-4-fe/f-bu†y!-6-bromomethylphenoi (3.52 g) in THF (26 ml); Ν,Ν'- dimethylethylenediamine (573 mg) in THF (13 ml); Et_a (1.644 g). Yeilow foam (2.53 g, 83%). 1H N R (500 MHz, Chloroform-d) δ: 10.22, 7.58, 7.43, 3.68, 2.69, 2.29, 1.27. MS (ES+J: m/z: 489.2.

57

Syn eses of 57

Genera! synthesis L. 2-formyi-4-fe/f-buty!-6-bromomethylphenoi (3.52 g) in THF (26 ml); Ν,Ν'- dimethyl-1 ,3-propanediamine (664.3 mg) in THF (13 mL); NEt_s (1.644 g). Yellow foam (2.84 g, 91 %). *H UMR {Sm MHz, Chioroform-d) δ; 10.29, 7.61, 7,32 , 3.71, 2.55, 2.31, 1.83 - 1.79, 1.29, MS (ES*): m/z: 483.4.

58

Synthesis of 58

General synthesis L.2-formy!-4-te/f-buiyi-6-bromomethyiphenoi (1.71 g) in THF (20 ml); Ν,Ν'- diisopropylethylenediarnine (500 mg) in THF (10 mL); HEt₃ (798 mg). Ye How foam (1.19 g, 72 %).

'H N R (600 MHz, Chioroform-d) δ: 10.16, 7.54, 7.46, 3.81, 2,89, 2,59, 1.29, 0.88. S (ES+): fz: S25.4; MS (ES-) rn/ : 523.3.

59

Synt e es of §9

General synthesis L.2-formyi-4-fe/f-butyi-6-bromomethyiphenoi (1.71 g) in THF (20 mL); Ν,Ν'- diisopropyl-1 ,3-propanediamine (500 mg) in THF (10 mL); NEt₃ (798 mg). Yeliow foam (1.53 g, 90 %).

¹H N R (500 MHz, Chioroform-d) δ: 10.36, 7.62, 7.28, 3.77, 3.06, 2.51, 1.81 - 1.74, 1.27, 1.07. MS (£S*|: rn/z; 539.4; MS (ES~); rn/z: 537.4.

General synthesis M The dialdehyde was dissolved in EtOH and the corresponding primary amine was added to the soiution. The solution was stirred for a few minutes at room temperature, in some oases, bright yeiiow precipitate was observed, and the product was ooiieoted by titration. Where such product precipitation did not occur, the reaction was left to stir 2-18 hours, then anhydrous Na₂S0₄ was added before the end of the reaction, and the product was obtained after filtration and removal of the solvent

60a

Synthesis of 80a

General synthesis . Dialdehyde 56 (633 mg); Ethyiamine (2 in THF, 1.35 mL); EtOH (13 ml): Na₂S0₄ (960 mg). Yeiiow oit (606 mg, 86 %).

¹H NMR (500 MHz, Chloroform-d) δ: 13.68, 8.37, 7.37, 7.16, 3.69 ~ 3.50, 2.68, 2.27, 1.31 - 1.29. MS iES-^;i: m/z: 5.23,4.

60b

Synthesis oi 60b

Generai synthesis . Dialdehyde 56 (633 mg); iso-Propylamine (160 mg); EtOH (13 ml); Na₂S0₄ (960 mg). Yellow foam (624 mg, 84 %). *H N R (508 MHz, Chiorerform-d) δ: 1377, 8.36, 7,38, 7.14, 3,60, 3,58 - 3,44, 2.68, 2,23, 1 ,29, 1 .27. !V!S (ES*): m/z: 551 .4.

60c

General synthesis . Dia!dehyde §8 {833 mg); tert-Butylamine (198 mg); EtOH (13 ml); Na₂S0 (960 mg). Yellow foam (631 mg, 81 %). ¹H NMR {500 MHz, Chloroform-d) δ: 14.46, 8.33, 7.39, 7.14, 3.61 , 2.68, 2 ,28, 1 ,32, 1 .29. S (ES+): m/z: 579.5 ,

60d

Synthesis of 60d

General synthesis . Diaidehyde SS (194 mg); benzylamine (89 mg); EtOH (5 ml); Na₂S0₄ (293 mg). Yellow sticky oil (243 mg, 91 %).

¹H NMR (500 MHz, Chloroform-d) δ: 13.44, 8.48, 7.44 - 7.20, 4,78, 3.81 , 2.66, 2.26, 1 .28. MS (£S*|: m/z: 647.4.

General synthesis M . Diaidehyde 57 (71 0 nig); Ethyiamine (2M in THF, 1 .4 / mL); EiOH (10 mL); Na₂SO, (1 .05 g). Yellow oil (857 mg, 83 %).

¹H NM (500 MHz, Ch!oroform-d) δ: 13.72, 8.36, 7.37, 7.16, 3.84 ~ 3.52, 2.47, 2.26, 1 .95 - 1 .76, 1 .29. MS (ES+): m/z: 537.4.

6^{1 b}

Synthesis of 81 b

Genera! synthesis . Diaidehyde 57 (710 mg); iso-Propyiamine (1 /4 mg); EtOH (10 mL); Na-,_:S0 (1 .05 g). Yellow foam (692 mg, 83 %).

Ή NMR (SOO MHz, Chiorerform-d) δ: 13.78, 8.38, 7,38, 7.14, 3,57, 3.56 - 3.48, 2.47, 2,26, 1 .84, 1 .29, 1 ,27. MS (ES+): m/z: 565,4.

61c

Synthesis of 61c

General synthesis . Diaidehyde ST (710 mg); tert-Butylamine (216 mg); EtOH (10 mL); Na_zS0₄ (1.05 g). Yellow foam (681 mg, 78 ).

^! ~d} δ: 14.46, 8.33, 7.39, 7.14, 3,57, 2.47, 2.26, 1.93 -- 1.78,

62

Synthesis of 62

General synthesis . Diaidehyde 58 (500 mg); Eihyiamine (2M in THF, 1.5 mL); EtOH (10 mL); Na₂SOi (677 mg). Yellow oil (5 0 mg, 92 %).

¹H NMR (500 MHz, Chloroform-d) δ: 13,55, 8.38, 7.68 - 7,63, 7.15, 3.79, 3,60, 2.94 - 2.86, 2.57, 1.29, 0.89. MS (£S*|: m/z: 579.4.

63

S nt e is of 63

General synthesis . Diaidehyde S3 (500 mg); Eihyiamine (2 in THF, 1 .5 mL): EtOH (10 mL); Na₂SG (659 mg). Yellow oil (498 rng, 91 %),

¹ H N R (500 MHz, Chioroform-d) δ: 13.71 , 8.40, 7.55, 7.18, 3.63, 3.60, 2.99 - 2.92, 2.48, 1 .86 -- 1 .55, 1 .29, 1 .00. MS <ES+): m/z: 593.5.

Synthesis of 84

Diaidehyde 56 (633 mg) was dissolved in MeCN (10 mL) and Ni(OAc)_?..4H₂0 (871 mg) was added. A deep green solution formed, it was left to stir overnight. The complex was isolated as bright green soild after solvent remova! (Yield 100%).

MS (ES+): m/z: 641 .2.

Genera! synthesis N

The iigand was dissolved in MeCN, Ni(OAc)-,_:.4H₂0 was added and the suspension was stirred until it turned into a clear solution. Complex solutions were green to green-brown . The catalysts were obtained as solids after removal of the solvent .

65a

sss of 85a

General synthesis N. Ligand 60a (806 mg); Ni(OAc)₂.4H₂0 (577 mg); eCN (10 ml). Green solid (763 mg, 87%).

(ES*): m/z: 654.2, 668.2, 681 .2, 695.2

65b

Synt e es of 8Sb

General synthesis . The ligand S0d (243 mg) was dissolved in MeCN, i(OAo)₂.4H₂0 (187 mg) was added as a solid. The reaction was stirred overnight at room temperature, a green- brown solution was obtained. The solvent was removed, the green residue was taken up in DCM and washed with H₂0. To the combined organic extracts was added MeOH and drying agent, and ail solvents were removed after filtration. MS (ES*|: m/z: 805.2, 819.2.

Syn eses of 86a

General synthesis N. Ligand 81a (857 mg); Ni(OAc)₂.4H₂0 (808 mg); MeCN (10 ml). Green solid (847 mg, 90%).

MS (ES+): 668.2, 682.2, 695.2, 709.2.

6⁷

Synthesis of 87

General synthesis . Dia!dehyde 57 (710 mg); Ethyiamine (2M in THF, 2.8 rnL); Et OH (10 mL); Na₂S0₄ (1.05 g); NaBH (218 mg). After filtration from Na₂S0₄, NaBH₄ was added in portions. Workup by removing the solvent, extraction with DCM/aq. NaHCO_? extraction. Off- white foam (Yield; 100%),

¹H N R (500 MHz, Chloroform-d) δ: 7.09, 6.91 , 3.80, 3.65, 2.70, 2.50, 2.27, 1.91 - 1.77,

1 .26, 1 .14. !V!S (ES*): m/z: 541 ,4.

68

Syrs esss of 88

The iigand 67 (715 mg) was dissolved in eCN (10 mL), Ni(OAc)₂.4H₂0 (732 mg) was added as a solid and the reaction was stirred at room temperature overnight. A mint green precipitate formed, which was collected and washed with H₂0. (505 mg).

MS IBS*}: rn/z: 699.2, 713.2. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. Each feature disclosed in this specification (including any accompanying claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features. The invention is not restricted to the details of the foregoing embodiment(s). The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

Claims

1. A polymerisation process for the reaction of:

(a) carbon dioxide with an epoxide; and/or

(b) an anhydride with an epoxide,

formula (I) wherein R¹ and R² are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine group, -NCR¹³R¹⁴, an amine, an ether -OR¹⁵, -R¹⁸OR¹⁷, an ester group - OC(0)R¹⁰ or -C(0)OR¹⁰, an amido group -NR⁹C(0)R⁹ or -C(0)-NR⁹(R⁹), -COOH, -C(0)R¹⁵, -OP(0)(OR¹⁸)(OR¹⁹) ,-P(O)R²⁰R²¹, -P(0)(OR)(OR), -OP(0)R(OR), a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;

R⁹, R ⁰, R¹³, R ⁴, R ⁸, R¹⁹, R²⁰ and R²¹ are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group;

E¹ is C, E² is O, S or NH or E¹ is N and E² is O; E³ is N, NR⁵, O or S, wherein when E³ is N, is , and when E³ is NR⁵, O or S, is ;

X, when present, is independently selected from OC(0)R , OS0₂R^x, OSOR^x, OSO(R^x)₂, S(0)R^x, OR , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, nitro, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl; m and n are independently integers selected from the range 0-3, such that the sum of m and n is 0-4;

each G is independently absent or a neutral or anionic donor ligand which is a Lewis base; Y¹ and Y² are independently a neutral or anionic donor group capable of donating a lone pair to the metal M²;

1 and M² are independently selected from Zn(ll), Cr(ll), Co(ll), Cu(ll), Mn(ll), Mg(ll), Ni(ll), Fe(ll), Ti(ll), V(ll), Cr(lll), Co(lll), n(lll), Ni(lll), Fe(lll), Ca(ll), Ge(ll), Al(lll), Ti(lll), V(lll), Ge(IV), Y(lll), Sc(lll) or Ti(IV).

2. A catalyst of formula (II):

formula (II) wherein R¹ and R² are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine group, -NCR¹³R¹⁴, an amine, an ether -OR¹⁵, -R¹⁶OR¹⁷, an ester group - OC(0)R¹⁰ or -C(0)OR¹⁰, an amido group -NR⁹C(0)R⁹ or -C(0)-NR⁹(R⁹), -COOH, -C(0)R¹⁵, -OP(0)(OR¹⁸)(OR¹⁹) ,-P(O)R²⁰R²¹, -P(0)(OR)(OR), -OP(0)R(OR), a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;

R⁹, R¹⁰, R¹³, R¹⁴, R¹⁸, R¹⁹, R²⁰ and R²¹ are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group;

E¹ is C, E² is O, S or NH or E¹ is N and E² is O;

R⁵ is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkylC(0)OR¹°, -alkylnitrile, or alkylaryl;

X, when present, is independently selected from OC(0)R^x, OS0₂R^x, OSOR , OSO(R^x)₂, S(0)R^x, OR , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, nitro, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl; m and n are independently integers selected from the range 0-3, such that the sum of m and n is 0-4;

each G is independently absent or a neutral or anionic donor ligand which is a Lewis base; Y¹ and Y² are independently a neutral or anionic donor group capable of donating a lone pair to the metal ² selected from a group with the lone pair donated by a non-aromatic nitrogen atom, a group with the lone pair donated by a carbene carbon atom, a group with the lone pair donated by a carbonyl oxygen atom and a group with the lone pair donated by a carboxylate oxygen atom;

M¹ and M² are independently selected from Zn(ll), Cr(ll), Co(ll), Cu(ll), n(ll), Mg(ll), Ni(ll), Fe(ll), Ti(ll), V(ll), Cr(lll), Co(lll), n(lll), Ni(lll), Fe(lll), Ca(ll), Ge(ll), Al(lll), Ti(lll), V(lll), Ge(IV), Y(lll), Sc(lll) or Ti(IV).

3. A polymerisation process for the reaction of (a) carbon dioxide with an epoxide; and/or

(b) an anhydride with an epoxide,

wherein the process is optionally carried out in the presence of a chain transfer agent and a catalyst according to claim 2.

4. A process according to claim 1 , wherein the atom of the Y¹ and/or Y² group that donates the lone pair is a hetero atom selected from oxygen, nitrogen or sulphur or a carbene carbon, more typically by a nitrogen or oxygen atom, most typically by a nitrogen atom.

5. A process according to any of claims 1 or 4, wherein Y¹ and Y² are independently selected from O, S, -^~NC(0)R¹⁰, - C(0)NR¹⁰, -C(0)0^", -C(0)OR¹⁰, -C(0)R¹⁰ , - C(R¹⁰)₂C(O)N(R¹⁰)₂, optionally substituted heteroaliphatic such as -OR¹⁰, -SR¹⁰, - NR¹⁰, - N(R¹⁰)₂, -C(R¹⁰)₂N(R¹⁰)₂, -C(R¹⁰)=N(R¹⁰), or optionally substituted heteroalicyclic or heteroaryl or an optionally substituted carbene structure, wherein R¹⁰ is independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group, more preferably, Y¹ and Y² are independently selected from O^", S^", -OR¹⁰, -SR¹⁰, - N(R¹⁰), - N(R¹⁰)₂, -C(R¹⁰)₂N(R¹⁰)₂, -C(R¹⁰)=N(R¹⁰), ^"N(R¹⁰)C(O)R¹⁰, -C(0)0, -C(0)OR¹⁰, C(0)R¹⁰ or optionally, imidazoline, 'abnormal' imidazoline (wherein the 'abnormal' imidazoline has a positive and a negative charge on the heterocycle due to the position of the double bond), imidazolidine, pyrrolidine, pyrroline, triazoline, thiazoline oxazole, oxazoline, imidazoylidene, imidazolinylidene, thiazolylidene, oxazolylidene, triazolylidene, benzimidazolylidene, pyrrolidinylidene or 'abnormal imidazolylidene or Ν,Ν'-diamidocarbene, optionally substituted pyridine, imidazole, methyl imidazole, benzimidazole, pyrrole, triazole, thiazole, benzimidazoline, benzotriazole, wherein R¹⁰ is independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group, still more preferably, Y¹ and Y² are independently selected from O, -OR¹⁰, -N(R¹⁰)_2, .C(R¹⁰)₂N(R¹⁰)₂, - C(R¹⁰)=N(R¹⁰) -C(O)O^", -C(0)R¹⁰, optionally substituted imidazolylidene, benzimidazolylidene, imidazolinylidene, or pyrrole, most preferably, Y¹ and Y² are independently selected from O, - OCH₃ -C(=0)H, -CH₂N(CH₃)₂, -CH₂N(H)(CH₂CH(CH₃)₂), -CH=N(CH₂CH(CH₃)₂), -CH₂- piperidine or benzotriazine.

6. A process according to any of claims 1 or 4, wherein the lone pair donating atom of the Y¹ and Y² groups is independently attached directly to the remainder of the catalyst of formula (I), via a bond to the respective aryl group, or is attached to the remainder of the catalyst of formula (I) via a linking group attached to the respective aryl group, preferably, the linking group, when present in Y¹ and/or Y², is selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, more preferably, the linking group, when present in Y¹ and/or Y², is selected from optionally substituted alkylene, alkenylene, alkynylene or arylene, even more preferably optionally substituted alkylene of arylene, especially, the linking group, when present in Y¹ and/or Y², is optionally substituted C C₁₀ alkylene, more especially, optionally substituted C C₆ alkylene, even more especially optionally substituted C C₄ alkylene, most especially, methylene.

7. A catalyst according to claim 2 or a process according to claim 3, wherein Y¹ and Y² of formula (II) are independently be selected from - NC(0)R¹⁰, -C(0)N^"R¹⁰ , -C0₂ ^", -C(0)R¹⁰ - C(R¹⁰)₂C(O)N^~(R¹⁰), optionally substituted heteroaliphatic wherein at least one heteroatom is nitrogen such as - NR¹⁰, -N(R¹⁰)₂, -C(R¹⁰)₂N(R¹⁰)₂, -C(R¹⁰),N(R¹⁰), or optionally substituted heteroalicyclic wherein at least one heteroatom is nitrogen or an optionally substituted carbene structure such as imidazolylidene, benzimidazolylidene or imidazolinylidene, wherein R¹⁰ is independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group, more preferably, Y¹ and Y² are independently selected from - N(R¹⁰), -N(R¹⁰)₂, -C(R¹⁰)₂N(R¹⁰)₂, -C(R¹⁰)=N(R¹⁰), - NC(0)R¹⁰ or optionally substituted imidazoline, 'abnormal' imidazoline (wherein the 'abnormal' imidazoline has a positive and a negative charge on the heterocycle due to the position of the double bond), imidazolidine, pyrrolidine, pyrroline, triazoline, thiazoline oxazole, oxazoline, imidazoylidene, imidazolinylidene, thiazolylidene, oxazolylidene, triazolylidene, benzimidazolylidene, pyrrolidinylidene, 'abnormal imidazolylidene or Ν,Ν'-diamidocarbene, wherein R¹⁰ is independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group, still more preferably, Y¹ and Y² of formula (II) are independently be selected from -CH₂N(CH₃)₂, -CH₂N(H)(CH₂CH(CH₃)₂), -CH=NC(CH₃)₃, - CH=N(CH₂CH(CH₃)₂), -CH₂-piperidine, -CH=NC₆H₃(CH₃)₂, -CH=NCH(CH₃)₂, -CH₂N(C₄H₉)₂, - CH=NC₈H₂(CH₃)₃, -CH₂N(C₂H₅)₂, -C(CH₃)=NCH₂CH(CH₃)₂ , -CH(CH₃)NHCH₂CH(CH₃)₂, - CH₂-pyrrolidine, -CH₂-morpholine, imidazolylidene, 1-methyl-imidazolylidene, 1 -ethyl- imidazolinylidene , 1-isopropyl-imidazolylidene, 1 -methyl-benzimidazolylidene wherein in the non-carbene structures the lone pair is provided by the nitrogen and wherein in the carbene structures the Y group is connected via an unsubstituted ring nitrogen and the lone pair is provided by the carbene carbon, most preferably, Y¹ and Y² of formula (II) are independently selected from -CH₂N(CH₃)₂, -CH₂N(H)(CH₂CH(CH₃)₂), -CH=N(CH₂CH(CH₃)₂), or -CH₂- piperidine.

8. A catalyst according to claim 2 or a process according to claim 3, wherein the lone pair donating atom of the Y¹ and Y² groups of formula (II) may independently be attached directly to the remainder of the catalyst of formula (I), via a bond to the respective aryl group, or may be attached to the remainder of the catalyst of formula (I) via a linking group attached to the respective aryl group. Preferably, the linking group, when present in Y¹ and/or Y², is selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene. More preferably, the linking group, when present in Y¹ and/or Y², is selected from optionally substituted alkylene, alkenylene, alkynylene or arylene, even more preferably optionally substituted alkylene of arylene. Preferably, the linking group, when present in Y¹ and/or Y², is optionally substituted C₁-C₁₀ alkylene, more preferably optionally substituted C Ce alkylene, even more preferably optionally substituted C C alkylene, most preferably methylene. For the avoidance of doubt, when the lone pair donating atom of the in Y¹ and/or Y² groups is a carbene carbon, the carbene carbon is not attached directly to the remainder of the catalyst of formula (I).

9. A process according to claim 1 or 3-8 or or a catalyst according to any of claim 2, or 7-8, wherein the catalyst is according to formula (la):

formula (la) wherein R¹-R⁴, E¹ , E², E³, X, G, Y¹, Y², n, m, M¹ and M² of formula (la) are as defined for formula (I) or (II) respectively.

10. A process according to any of claims 1 , 3-9 or a catalyst according to any of claims 2 or 7-9, wherein M¹ and M² are independently selected from Zn(ll), Cr(lll), Co(ll), Mn(ll), Mg(ll), Fe(ll) or Fe(lll), most preferably from Zn(ll), Co(ll) or Mg(ll), preferably, at least one of M¹ or M² may be selected from Ni(ll), Ni(lll), Co(ll), Co(lll), Cr(ll), Cr(lll), Fe(ll), Fe(lll), Mn(lll), Al(lll), Zn(ll) or Mg(ll).

11. A process according to any of claims 1 , 3-10 or a catalyst according to any of claims 2 or 7-10, wherein M¹ and M² are different, preferably, M¹ or ² is Ni(ll) or Ni(lll) and the other of M¹ or ² is Fe(ll), Fe(lll), Cr(lll), Al(lll), g(ll), Zn(ll), Co(ll) or Co(lll), more preferably M¹ or 2 is Ni(ll) and the other of M¹ or M² is Mg(ll), Zn(ll), Co(ll), Co(lll) or Cr(lll) or alternatively, preferably, each occurrence of M¹ and ² is different and ¹ or M² is Zn(ll) and the other of 1 or M² is g(ll).

12. A process according to any of claims 1 , 3-10 or a catalyst according to any of claims 2 or 7-10, wherein each occurrence of M¹ and M² is the same preferably, M¹ and M² may be Ni(ll), Ni(lll), Fe(ll), Fe(lll), Mn(lll), Cr(ll), Cr(lll), Co(ll), Co(lll), Zn(ll) or Mg(ll), more preferably each occurrence of M¹ and M² may be Ni(ll), Co(ll), Co(lll), Zn(ll) or g(ll).

13. A process according to any of claims 1 , 3-12 or a catalyst according to any of claims 2 or 7-12, wherein X is independently selected from OC(0)R^x, OS0₂R^x, OSO(R^x)₂, OR^x, halide, nitrate, hydroxyl, carbonate, amido or optionally substituted aliphatic, heteroaliphatic (for example silyl), alicyclic, heteroalicyclic, aryl or heteroaryl and R_x is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl, preferably, X is OCOCH₃, OCOCF₃, OSO₂C₇H₇, OSO(CH₃)₂, Et, Me, PhOEt, O e, OiPr, OtBu, CI, Br, I, F, N(iPr)₂ or N(SiMe₃)₂.

14. A process according to any of claims 1 , 3-13 or a catalyst according to any of claims 2 or 7-13, wherein each occurrence of E may be the same or different, preferably, wherein each occurrence of E¹ is the same.

15. A process according to any of claims 1 , 3-14 or a catalyst according to any of claims 2 or 7-14, wherein each occurrence of E² may be the same or different, preferably, wherein each occurrence of E² is the same.

16. A process according to any of claims 1 , 3-15 or a catalyst according to any of claims 2 or 7-15, wherein E¹ is C and E² is O, S or NH, more preferably E¹ is C and E² is O.

17. A process according to any of claims 1 , 3-16 or a catalyst according to any of claims 2 or 7-16, wherein each occurrence of E³ may be the same or different, preferably, wherein each occurrence of E³ is the same.

18. A process according to any of claims 1 , 3-17 or a catalyst according to any of claims 2 or 7-17, wherein the groups R¹ and R² may be the same or different, preferably, R¹ and R² are independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, heteroalicyclic, alkoxy, aryloxy or alkylthio, even more preferably, R² is hydrogen and R¹ is independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and optionally substituted alkyl, alkenyl, aryl, heteroaryl, heteroalicyclic, alkoxy, aryloxy, alkylthio, arylthio, such as hydrogen, C_halky! (e.g. haloalkyl), alkoxy, aryl, halide, nitro, sulfonyl, silyl and alkylthio, for example, ,t-butyl, n-butyl, i-propyl, methyl, piperidinyl, methoxy, hexyl methyl ether, -SCH₃, -S(C₆H₅), H, nitro, trimethylsilyl, methylsulfonyl (-S0₂CH₃), triethylsilyl, halogen or phenyl.

19. A process according to any of claims 1 , 3-18 or a catalyst according to any of claims

2 or 7-18, wherein each occurrence of the groups R1 and R2 may be the same or different, preferably, each occurrence of R1 and R2 are independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, heteroalicyclic, alkoxy, aryloxy or alkylthio, even more preferably, R² is hydrogen and R¹ is independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and optionally substituted alkyl, alkenyl, aryl, heteroaryl, heteroalicyclic, alkoxy, aryloxy, alkylthio, arylthio, such as hydrogen, C_{1 6}alkyl (e.g. haloalkyl), alkoxy, aryl, halide, nitro, sulfonyl, silyl and alkylthio, for example, ,t-butyl, n-butyl, i-propyl, methyl, piperidinyl, methoxy, hexyl methyl ether, -SCH₃, -S(C_BH₅), H, nitro, trimethylsilyl, methylsulfonyl (-S0₂CH₃), triethylsilyl, halogen or phenyl.

20. A process according to any of claims 1 , 3-19 or a catalyst according to any of claims 2 or 7-19, wherein each occurrence of R¹ can be the same or different, preferably, each occurrence of R¹ is the same and is preferably selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, heteroalicyclic, alkoxy, aryloxy, or alkylthio, more preferably, both occurrences of R¹ are the same, and are selected from halide, sulfoxide, silyl, and an optionally substituted alkyl, heteroaryl or alkoxy, still more preferably, both occurrences of R¹ are the same, and are selected from H, alkyl, aryl, alkoxy, trialkylsilyl such as triethylsilyl, or halide, more preferably still, both occurrences of R¹ are the same, and are selected from H, alkyl, phenyl, halide or trialkylsilyl, most preferably, both occurrences of R¹ are the same, and are selected from H, methyl, ethyl, n-propyl, i-propyl n-butyl, t-butyl, t-amyl or t-octyl.

21. A process according to any of claims 1 , 3-20 or a catalyst according to any of claims 2 or 7-20, wherein R³ is selected from -CH₂C(CH₃)₂CH₂-, -CH₂CH₂CH₂-, -CH₂CH(CH₃)CH₂-, - CH2C(CH2C6H5)2CH2~, ^— (ΟβΗ, )-, -CH2CH2-, -CH2^_CH2CH2CH2", -CH2CH₂N(CH3)CH2CH₂~, ^— (C₆H₁₀)- or -CH₂CH₂CH(C₂H₅)-, still more preferably R³ is selected from -CH₂C(CH₃)₂CH₂-, - CH₂CH₂-, -CH₂CH₂CH₂-, -CH₂CH(CH₃)CH₂~, -CH₂C(CH₂C₅H₅)₂CH₂~, -CH₂CH₂CH(C₂H₅)-, - CH₂CH₂CH₂CH₂-, more preferably still, R³ is selected from -CH₂C(CH₃)₂CH₂-, CH₂CH₂CH₂-, -CH₂CH(CH₃)CH₂- and -CH₂C(C₂H₅)₂CH₂-.

22. A process according to any of claims 1 , 3-21 or a catalyst according to any of claims 2 or 7-21 , wherein R⁴ is selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, phenyl and trifluoromethyl, preferably hydrogen, methyl or trifluoromethyl, even more preferably, each R⁴ is hydrogen.

23. A process according to any of claims 1 , 3-22 or a catalyst according to any of claims 2 or 7-22, wherein the R⁵, when present, is independently selected from hydrogen or optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyi, heteroalkenyl, heteroalkynyl, heteroaryl, -alkylC(0)R¹⁰ or -alkylnitrile, more preferably selected fromH, Me, Et, Bn, iPr, tBu or Ph.

24. A process according to claim 1 , wherein the catalysts of formula (I) are:

111

112

113

114

115

116

25. A catalyst according to claim 2, or a process according to claim 3, wherein the catalysts of formula (II) are:

118

the presence of a further catalyst being a double metal cyanide (DMC) catalyst.

27. A process according to claim 26, wherein the first two of the at least two metal centres in the double metal cyanide (DMC) catalyst are represented by M' and ", wherein ' is selected from Zn(ll), Ru(ll), Ru(lll), Fe(ll), Ni(ll), Mn(ll), Co(ll), Sn(ll), Pb(ll), Fe(lll), Mo(IV), Mo(VI), Al(lll), V(V), V(VI), Sr(ll), W(IV), W(VI), Cu(ll), and Cr(lll), preferably selected from Zn(ll), Fe(ll), Co(ll) and Ni(ll), even more preferably Zn(ll) and " is selected from Fe(ll), Fe(lll), Co(ll), Co(lll), Cr(ll), Cr(lll), n(ll), Mn(lll), Ir(lll), Ni(ll), Rh(lll), Ru(ll), V(IV), and V(V), preferably selected from Co(ll), Co(lll), Fe(ll), Fe(lll), Cr(lll), Ir(lll) and Ni(ll), more preferably selected from Co(ll) and Co(lll) and optionally, a further metal centre(s) is present, the said further metal centre being selected from the definition of ' or M".

28. A process according to any of claims 1 or 3-27 or a DMC catalyst combination with a catalyst according to any of claims 2 or 7-24, wherein the DMC catalyst has a formula:

M'_d[M"e(CN)_f]_g wherein M' and M" are as defined above, d, e, f and g are integers, and are chosen such that the DMC catalyst has electroneutrality.

29. A process according to claim 28 wherein the DMC catalyst may have the following formula:

M'_d[M"e(CN)_f]_g ^■ hM"'X" ^■ jR^c■ kH₂0 ^■ IH_rX"' wherein M', M", X'", d, e, f and g are as defined above. M'" can be M' and/or M". X" is an anion selected from halide, oxide, hydroxide, sulphate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, preferably X" is halide; i is an integer of 1 or more, and the charge on the anion X" multiplied by i satisfies the valency of M'"; r is an integer that corresponds to the charge on the counterion X'"; R^c is a complexing agent, and may be as defined above, for example, R^c may be a (poly)ether, a polyether carbonate, a polycarbonate, a poly(tetramethylene ether diol), a ketone, an ester, an amide, an alcohol (e.g. a C^s alcohol), a urea and the like, such as propylene glycol, polypropylene glycol, (m)ethoxy ethylene glycol, dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyme, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, 3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1 -pentyn-3-ol, for example, R° may be tert-butyl alcohol, dimethoxyethane, or polypropylene glycol; h, j, k and/or I are an integer between 0 and 20.

30. A process according to any of claims 1 or 3-29, wherein the chain transfer agent is selected from water or a compound of formula (III):

each W is independently selected from a hydroxyl, amine, thiol or carboxylate group; and a is an integer which is at least 2.

31. A process according to claim 30, wherein the chain transfer agent (CTA) may be water or a compound which has two or more groups independently selected from hydroxyl (- OH), amine (-NHR^W), thiol (-SH) or carboxylate (-C(O)OH), wherein R^w is hydrogen, optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl, or combinations thereof (i.e. aliphaticaryl, aliphaticheteroaryl, heteroaliphaticaryl, etc).

32. A process according to claim 30 or 31 , wherein the chain transfer agents are selected from water, mono-alcohols (i.e. alcohols with one OH group, for example, 4- ethylbenzenesulfonic acid, methanol, ethanol, propanol, butanol, pentanol, hexanol, phenol, cyclohexanol), diols (for example, 1 ,2-ethanediol, 1 -2-propanediol, 1 ,3-propanediol, 1 ,2- butanediol, 1 -3-butanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,2-diphenol, 1 ,3- diphenol, 1 ,4-diphenol, catechol and cyclohexenediol), triols (glycerol, benzenetriol, 1 ,2,4- butanetriol, tris(methylalcohol)propane, tris(methylalcohol)ethane, tris(methylalcohol)nitropropane, trimethylolpropane, preferably glycerol or benzenetriol), tetraols (for example, calix[4]arene, 2,2-bis(methylalcohol)-1 ,3-propanediol, di(trimethylolpropane)), polyols (for example, dipentaerythritol, D-(+)-glucose or D-sorbitol), dihydroxy terminated polyesters (for example polylactic acid), dihydroxy terminated polyethers (for example poly(ethylene glycol)), acids (such as diphenylphosphinic acid), starch, lignin, mono-amines (i.e. methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine), diamines (for example1 ,4-butanediamine), triamines, diamine terminated polyethers, diamine terminated polyesters, mono-carboxylic acids (for example, 3,5-di-tert-butylbenzoic acid), dicarboxylic acids (for example, maleic acid, malonic acid, succinic acid, glutaric acid or terephthalic acid, preferably maleic acid, malonic acid, succinic acid, glutaric acid), tricarboxylic acids (for example, citric acid, 1 ,3,5-benzenetricarboxylic acid or 1 ,3,5-cyclohexanetricarboxylic acid, preferably citric acid), mono-thiols, dithoils, trithiols, and compounds having a mixture of hydroxyl, amine, carboxylic acid and thiol groups, for example lactic acid, glycolic acid, 3-hydroxypropionic acid, natural amino acids, unnatural amino acids, monosaccharides, disaccharides, oligosaccharides and polysaccharides (including pyranose and furanose forms), preferably, the chain transfer agent is selected from cyclohexene diol, 1 ,2,4-butanetriol, tris(methylalcohol)propane, tris(methylalcohol)nitropropane, tris(methylalcohol)ethane, tri(methylalcohol)propane, tri(methylalcohol)butane, pentaerythritol, poly(propylene glycol), glycerol, mono- and di- ethylene glycol, propylene glycol, 2,2-bis(methylalcohol)-1 ,3-propanediol, 1 ,3,5- benzenetricarboxylic acid, 1 ,3,5-cyclohexanetricarboxylic acid, 1 ,4-butanediamine, 1 ,6- hexanediol, D-sorbitol, 1 -butylamine, terephthalic acid, D-(+)-glucose, 3,5-di-tert-butylbenzoic acid, and water.

33. A process according to any of claims 1 or 3-32 wherein the epoxide is on a group which is aliphatic, including acyclic and alicyclic, or aromatic.

34. A process according to any of claims 1 or 3-33 wherein the epoxide include cyclohexene oxide, styrene oxide, unsubstituted or substituted alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, substituted cyclohexene oxides (such as limonene oxide, C₁₀H_1BO or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C^h^O), unsubstituted or substituted oxiranes (such as oxirane, epichlorohydrin, 2-(2- methoxyethoxy)methyl oxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyl oxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl oxirane (ME3MO), 1 ,2- epoxybutane, glycidyl ethers, glycidyl esters, glycidyl carbonates, vinyl-cyclohexene oxide, 3- phenyl-1 ,2-epoxypropane, 1 ,2- and 2,3-epoxybutane, isobutylene oxide, cyclopentene oxide, 2, 3-epoxy-1 ,2,3,4-tetrahydronaphthalene, indene oxide, and functionalized 3,5-dioxaepoxides or mixtures thereof.

35. A process according to any of claims 1 or 3-34, wherein the epoxide is a CrC₁₀ alkylene oxide.

36. A process according to any of claims 1 or 3-35, wherein the epoxide is a monosubstituted epoxide, preferably propylene oxide.

37. A process according to any of claims 1 or 3-36, wherein when the polymerisation process comprises the reaction of an anhydride with an epoxide, the anhydride may be any compound comprising an anhydride moiety in a ring system (i.e. a cyclic anhydride) and the epoxide may be any of the epoxides defined herein, preferably, the anhydrides have the following formula:

wherein m" is 1 , 2, 3, 4, 5, or 6 (preferably 1 or 2), each R^a1 , R^a2, R^a3 and R^a4 is independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl; or two or more of R^a1 , R^a2, R^a3 and R^a4 can be taken together to form a saturated, partially saturated or unsaturated 3 to 12 membered, optionally substituted ring system, optionally containing one or more heteroatoms, or can be taken together to form a double bond. Each Q is independently C, O, N or S, preferably C, wherein R^a3 and R^a4 are either present, or absent, and can either be = or , according to the valency of Q. It will be appreciated that when Q is C, and is , R^a3 and R^a4 (or two R^a4 on adjacent carbon atoms) are absent, more preferably, the anhydrides are selected from those set out below:-

38. A process according to any of claims 1 or 3-37, wherein the polymerisation process is carried out at a pressure of 1 to 100 atmospheres, preferably at 1 to 40 atmospheres, such as at 1 to 20 atmospheres, more preferably at 1 or 10 atmospheres.

39. A process according to any of claims 1 or 3-38, wherein the polymerisation process is carried out at a temperature of about 0°C to about 250°C, preferably from about 40°C to about 160°C, even more preferably from about 50°C to about 120°C.

40. A process according to any of claims 1 or 3-39, wherein the polymerisation process is carried out in the reaction of carbon dioxide with an epoxide at a catalytic mol:mol loading of about 1 :1 ,000-100,000 catalyst:epoxide, more preferably about 1 :1 ,000-300,000 catalyst:epoxide, even more preferably about 1 :10,000-100,000, and most preferably about 1 :50,000-100,000 catalyst:epoxide and in the reaction of an anhydride with an epoxide at a catalytic loading of about 1 :1 ,000-300,000 catalysttotal monomer content, more preferably about 1 :10,000-100,000 catalyst:total monomer content, most preferably about 1 :50,000- 100,000 catalyst:total monomer content.

41 A process according to any of claims 28-40 wherein the mass ratio of the catalyst of formula (I) and (II) to the DMC catalyst may be in the range of from about 300:1 to about 0.1 :1 , for example, from about 120:1 to about 0.25:1 , such as from about 40:1 to about 0.5:1 , e.g. from about 30:1 to about 0.75:1 such as from about 20:1 to about 1 :1 , for example from about 10:1 to about 2:1 , e.g. from about 5:1 to about 3:1 .

42. A process according to any of claims 1 or 3-41 wherein a starter compound may be present in molar ratios of about 200:1 to about 1 :1 , for example, from about 175:1 to about 5:1 , such as from about 150:1 to about 10:1 , e.g. from about 125:1 to about 20:1 , for example, from about 50:1 to about 20:1 , relative to the catalyst of formula (I) and (II).

43. A polymer produced by the process of claim 1 or 3-42.

44. A polymer according to claim 43 selected from polycarbonates, polyether carbonate polyols or polyester polyols.

45. A polymer according to any of claims 43 or 44, wherein the number-average molecular weight (M_n) of the polymer products is from about 1 ,000 g/mol to about 100,000 g/mol.

46. A polymer according to any of claims 43-45, wherein the polyether carbonate polyols and polyester polyols having a M_n of from about 200 g/mol to about 20,000 g/mol, preferably less than about 10,000 g/mol.

47. A polymer according to any of claims 43-46, wherein the polymer products have a polydispersity index (PDI) of less than about 2, preferably less than about 1.5, even more preferably less than about 1 .2.

48. A polyurethane or other higher polymer produced from polycarbonates, polyether carbonate polyols or polyester polyols according to any of claims 43-47.