WO2019116006A1 - Polymerisation of cyclic esters and cyclic amides - Google Patents
Polymerisation of cyclic esters and cyclic amides Download PDFInfo
- Publication number
- WO2019116006A1 WO2019116006A1 PCT/GB2018/053539 GB2018053539W WO2019116006A1 WO 2019116006 A1 WO2019116006 A1 WO 2019116006A1 GB 2018053539 W GB2018053539 W GB 2018053539W WO 2019116006 A1 WO2019116006 A1 WO 2019116006A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkoxy
- phenoxy
- benzyloxy
- optionally substituted
- halo
- Prior art date
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- 150000003950 cyclic amides Chemical class 0.000 title claims abstract description 28
- 125000004122 cyclic group Chemical group 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims abstract description 80
- -1 cyclic ester Chemical class 0.000 claims abstract description 76
- 230000008569 process Effects 0.000 claims abstract description 76
- VNEACLJMGRLSEJ-UHFFFAOYSA-N CC1=C(C)C2=C(C)C(C)=C(C)C2=C1C Chemical compound CC1=C(C)C2=C(C)C(C)=C(C)C2=C1C VNEACLJMGRLSEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 13
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 343
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 132
- 125000005843 halogen group Chemical group 0.000 claims description 125
- 125000001424 substituent group Chemical group 0.000 claims description 124
- 125000003118 aryl group Chemical group 0.000 claims description 108
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 102
- 125000000217 alkyl group Chemical group 0.000 claims description 100
- 125000004104 aryloxy group Chemical group 0.000 claims description 98
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 95
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 92
- 239000002904 solvent Substances 0.000 claims description 84
- 150000001875 compounds Chemical class 0.000 claims description 75
- 229910052765 Lutetium Inorganic materials 0.000 claims description 55
- 229910052727 yttrium Inorganic materials 0.000 claims description 55
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 49
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 49
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 49
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 46
- 125000003342 alkenyl group Chemical group 0.000 claims description 45
- 125000000304 alkynyl group Chemical group 0.000 claims description 45
- 229910052684 Cerium Inorganic materials 0.000 claims description 34
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 34
- 229910052746 lanthanum Inorganic materials 0.000 claims description 34
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 34
- 229910052706 scandium Inorganic materials 0.000 claims description 34
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 34
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 33
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 30
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 29
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 29
- 125000001246 bromo group Chemical group Br* 0.000 claims description 28
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000012986 chain transfer agent Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 150000002596 lactones Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003951 lactams Chemical class 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 8
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 230000009881 electrostatic interaction Effects 0.000 description 3
- 150000004820 halides Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 101100343498 Mus musculus Lipn gene Proteins 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical compound [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 description 2
- 238000004807 desolvation Methods 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000003019 stabilising effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- YBGCOFSXTRUWOR-UHFFFAOYSA-N [Th]CC1=CC=CC=C1 Chemical compound [Th]CC1=CC=CC=C1 YBGCOFSXTRUWOR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000599 controlled substance Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/14—Other (co) polymerisation, e.g. of lactides or epoxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/36—Yttrium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
Definitions
- the present invention relates to a catalytic process for the ring opening polymerisation (ROP) of a cyclic ester or a cyclic amide. More particularly, the catalytic process employs, as catalysts, rare earth metal complexes having permethylpentalene or (hydro)permethylpentalene ligands.
- ROP ring opening polymerisation
- PLAs Poly(lactic acids)
- PLAs Poly(lactic acids)
- PLAs are both biodegradable and biocompatible, they are of equal value to the field of medicine, wherein their versatile physical properties make them suitable for in vivo applications (e.g. as media for controlled drug delivery devices).
- a process for the ring opening polymerisation (ROP) of a cyclic ester or a cyclic amide comprising the step of contacting a compound having a structure according to formula (I) defined herein with one or more cyclic esters or cyclic amides.
- alkyl refers to a straight or branched chain alkyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms. This term includes reference to groups such as methyl, ethyl, propyl (n-propyl or isopropyl), butyl (n-butyl, sec-butyl or tert-butyl), pentyl, hexyl and the like. In particular, an alkyl may have 1 , 2, 3 or 4 carbon atoms.
- alkenyl refers to straight or branched chain alkenyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms.
- This term includes reference to groups such as ethenyl (vinyl), propenyl (allyl), butenyl, pentenyl and hexenyl, as well as both the cis and trans isomers thereof.
- alkynyl refers to straight or branched chain alkynyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms.
- the term includes reference to alkynyl moieties containing 1 , 2 or 3 carbon-carbon triple bonds (CoC). This term includes reference to groups such as ethynyl, propynyl, butynyl, pentynyl and hexynyl.
- alkoxy refers to -O-alkyl, wherein alkyl is straight or branched chain and comprises 1 , 2, 3, 4, 5 or 6 carbon atoms. In one class of embodiments, alkoxy has 1 , 2, 3 or 4 carbon atoms. This term includes reference to groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, hexoxy and the like.
- aryl refers to an aromatic ring system comprising 6, 7, 8, 9 or 10 ring carbon atoms.
- Aryl is often phenyl but may be a polycyclic ring system, having two or more rings, at least one of which is aromatic. This term includes reference to groups such as phenyl, naphthyl and the like.
- aryloxy refers to -O-aryl, wherein aryl has any of the definitions discussed herein. Also encompassed by this term are aryloxy groups in having an alkylene chain situated between the O and aryl groups.
- halogen or“halo” as used herein refers to F, Cl, Br or I. In a particular, halogen may be F or Cl, of which Cl is more common.
- substituted as used herein in reference to a moiety means that one or more, especially up to 5, more especially 1 , 2 or 3, of the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of the described substituents.
- optionally substituted as used herein means substituted or unsubstituted.
- substituents are only at positions where they are chemically possible, the person skilled in the art being able to decide (either experimentally or theoretically) without inappropriate effort whether a particular substitution is possible.
- amino or hydroxy groups with free hydrogen may be unstable if bound to carbon atoms with unsaturated (e.g. olefinic) bonds.
- substituents described herein may themselves be substituted by any substituent, subject to the aforementioned restriction to appropriate substitutions as recognised by the skilled person.
- cyclic esters and “cyclic amides” as used herein refer to heterocycles containing at least one ester or amide moiety. It will be understood that lactides, lactones and lactams are encompassed by these terms.
- the first aspect of the invention provides a process for the ring opening polymerisation (ROP) of a cyclic ester or a cyclic amide, the process comprising the step of contacting a compound having a structure according to formula (I) shown below with one or more cyclic esters or cyclic amides: wherein
- M 1 and M 2 are each independently a group 3 metal or a lanthanide
- X 1 is selected from halo, (1 -6C)alkoxy, aryl(1 -3C)alkoxy and aryloxy, wherein the (1 -6C)alkoxy, aryl(1 -3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1 -5C)alkyl, (2-5C)alkenyl, (2-5C)alkynyl and (1-5C)alkoxy,
- X 2 is absent, or is selected from halo, (1 -6C)alkoxy, aryl(1 -3C)alkoxy and aryloxy, wherein the (1 -6C)alkoxy, aryl(1 -3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-5C)alkyl, (2- 5C)alkenyl, (2-5C)alkynyl and (1-5C)alkoxy,
- X 2 is a neutral ligand (e.g. a complexed solvent)
- Li and l_2 are each independently selected from permethylpentalene and (hydro)permethylpentalene.
- the compounds of formula (I) are noticeably more active.
- the rare earth metal complexes of formula (I) exhibit a stark increase in catalytic activity over zirconium-based analogues.
- M 1 and M 2 may be independently selected from any group 3 metal or any lanthanide. It will be understood that the compounds of formula (I) are neutral (i.e. they carry no net charge). Therefore, M 1 and M 2 must each have a complete coordination sphere of charge balancing ligands X 1 , X 2 , L 1 and L 2 .
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium.
- M 1 and M 2 are each independently selected from yttrium and lutetium.
- M 1 and M 2 are the same.
- M 1 and M 2 are both yttrium or lutetium.
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy.
- X 1 may associated with M 1 and M 2 via electrostatic interactions, or by a mixture of covalent and electrostatic interactions, all of which are shown herein, for simplicity, as solid bonds.
- X 1 is halo, it associates with M 1 and M 2 as depicted below:
- X 1 is an oxygen-containing ligand, it associates with M 1 and M 2 as depicted below:
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy.
- X 1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1-4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy.
- X 1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1-4C)alkoxy.
- X 1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl.
- X 1 v selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl.
- X 1 is selected from chloro, benzyloxy, -0-2,6-dimethyl-phenoxy, -O- 2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy.
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent or another neutral ligand capable of completing the coordination sphere around M 1 /M 2 .
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent.
- X 2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1-4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent.
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent.
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent.
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent.
- X 2 is selected from chloro, benzyloxy, -0-2,6-dimethyl-phenoxy, -O- 2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy, or X 2 is a complexed solvent.
- X 2 is a solvent or another neutral ligand capable of completing the coordination sphere around M 1 /M 2 , it is suitably selected from an ether or pyridine. It will be understood that the solvent bonding is likely to proceed via an electrostatic interaction (rather than a covalent interaction) between the heteroatom of the solvent and MVM 2 ) via its heteroatom). More suitably, when X 2 is a complexed solvent, it is tetrahydrofuran.
- U and L 2 are independently selected from permethylpentalene and (hydro)permethylpentalene.
- Permethylpentalene (also denoted herein as Pn*) will be understood to refer to the following moiety:
- L 1 When L 1 is permethylpentalene, it typically coordinates to M 1 via 2 h 5 bonds. Similarly, when L 2 is permethylpentalene, it typically coordinates to M 2 via 2 h 5 bonds.
- X 2 is suitably a complexed solvent or another neutral ligand capable of completing the coordination sphere around MVM 2 . Alternatively, When U/L 2 is permethylpentalene, X 2 is absent.
- L 1 is (hydro)permethylpentalene
- L 2 is (hydro)permethylpentalene
- M 2 typically coordinates to M 2 via 1 h 5 bond.
- M 1 , M 2 , X 1 , X 2 , L 1 and L 2 may have any of the definitions recited hereinbefore.
- the compound of formula (I) has a structure according to formula (la) shown below:
- M 1 , M 2 , X 1 and X 2 have any of those definitions recited hereinbefore.
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from yttrium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy, -0-2,6-dimethyl-phenoxy, -0-2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1- 4C)alkoxy; and X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl; and
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl; and
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, benzyloxy, -0-2,6-dimethyl-phenoxy, -0-2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy; and X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and X 2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1- 4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl; and X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from yttrium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from yttrium and lutetium;
- X 1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from yttrium and lutetium;
- X 1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1- 4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran.
- M 1 and M 2 are each independently selected from yttrium and lutetium;
- X 1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (la), wherein
- M 1 and M 2 are each independently selected from yttrium and lutetium;
- X 1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb) shown below:
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from yttrium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy, -0-2,6-dimethyl-phenoxy, -0-2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1- 4C)alkoxy; and
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl; and
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl; and
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, benzyloxy, -0-2,6-dimethyl-phenoxy, -0-2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy;
- X 2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1- 4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
- X 1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from yttrium and lutetium;
- X 1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from yttrium and lutetium;
- X 1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from yttrium and lutetium;
- X 1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1- 4C)alkoxy, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from yttrium and lutetium;
- X 1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
- X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has a structure according to formula (lb), wherein
- M 1 and M 2 are each independently selected from yttrium and lutetium;
- X 1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl; and X 2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X 2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
- a complexed solvent e.g. pyridine or tetrahydrofuran
- the compound of formula (I) has any one of the following structures:
- the one or more cyclic esters or cyclic amides has a structure according to formula (II) shown below
- Q is selected from O or NR y , wherein R y is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl and (2-6C)alkynyl; and
- ring A is a 4-23 membered heterocycle containing 1 to 4 O or N ring heteroatoms in total, wherein the heterocycle is optionally substituted with one or more substituents selected from oxo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl and heteroaryl.
- Q is selected from O or NR y , wherein R y is selected from hydrogen, (1-3C)alkyl, (2-3C)alkenyl or (2-3C)alkynyl.
- Q is O.
- ring A is a 4-18 membered heterocycle containing 1 to 3 O or N ring heteroatoms in total, wherein the heterocycle is optionally substituted with one or more substituents selected from oxo, (1-6C)alkyl, (1-6C)alkoxy and aryl.
- ring A is a 4-, 6-, 7- or 16-membered heterocycle containing 1 to 3 O or N ring heteroatoms in total, wherein the heterocycle is optionally substituted with one or more substituents selected from oxo, (1-6C)alkyl, (1-6C)alkoxy and aryl.
- ring A does not contain any N ring heteroatoms.
- the cyclic ester or cyclic amide is a lactone.
- the cyclic ester or cyclic amide is a lactam.
- the cyclic ester or cyclic amide is a lactide (e.g. the cyclic diester of 2-hydroxypropionoic acid).
- the mole ratio of the compound of formula (I) to the cyclic ester or cyclic amide is 1 :5 to 1 :10,000.
- the mole ratio of the compound of formula (I) to the cyclic ester or cyclic amide is 1 :10 to 1 : 1000. More suitably, the mole ratio of the compound of formula (I) to the cyclic ester or cyclic amide is 1 :25 to 1 :250.
- the process is not conducted in a solvent.
- the process is conducted in a solvent selected from toluene, tetrahydrofuran and methylene chloride.
- the process is conducted for a period of 1 minute to 96 hours.
- the process is conducted for a period of 5 minute to 72 hours.
- the process is conducted at a pressure of 0.9 to 5 bar.
- the process is conducted at a pressure of 0.9 to 2 bar.
- the process is conducted at a temperature of 10 - 150°C.
- the process is conducted at a temperature 350°C (e.g. 50 - 150°C. More suitably, the process is conducted at a temperature greater than 360°C (e.g. 60 - 150°C). Most suitably, the process is conducted at a temperature greater than 370°C (e.g. 70 - 150°C or 70 - 120°C).
- the process is conducted in the presence of a chain transfer agent suitable for use in the ring opening polymerisation of a cyclic ester or cyclic amide.
- the chain transfer agent is a hydroxy-functional compound (e.g. an alcohol, diol or polyol). More suitably, the chain transfer agent is selected from the group consisting of tert-butanol, benzyl alcohol and iso-propanol.
- the compounds of formula (I) may be formed by any suitable process known in the art. Particular examples of processes for the preparing compounds for formula (I) are set out in the accompanying examples.
- M a has any of the identities discussed herein in relation to M 1 or M 2 .
- X is a halide (e.g. chloro).
- step i optionally reacting the product of step i with a compound of formula (B) shown below:
- R is (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1- 3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-5C)alkyl, (2-5C)alkenyl, (2-5C)alkynyl and (1- 5C)alkoxy.
- M a has any of the identities discussed herein in relation to M 1 or M 2 .
- X is a halide (e.g. chloro).
- step i optionally reacting the product of step i with a compound of formula (B) shown below:
- M b is an alkali metal (e.g. potassium), and
- R is (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1- 3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-5C)alkyl, (2-5C)alkenyl, (2-5C)alkynyl and (1- 5C)alkoxy.
- substituents selected from halo, (1-5C)alkyl, (2-5C)alkenyl, (2-5C)alkynyl and (1- 5C)alkoxy.
- any suitable solvent may be used in steps i and ii.
- the solvent used in step i and/or step ii may complex to M 1 /M 2 as neutral ligand, X 2 .
- the solvent used in steps i and ii is tetrahydrofuran.
- reaction conditions e.g. temperature, pressures, reaction times, agitation etc.
- Fig. 1 shows 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn * Y(p-CI)(thf)] 2 . * denotes residual protio solvent and bound thf, and + denotes residual tmeda.
- Fig. 2 shows 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*Lu(p-CI)(thf)] 2 . * denotes residual protio solvent and bound thf, and + denotes residual tmeda.
- Fig. 3 shows 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*(H)Y(p-CI)CI] 2 . * denotes residual protio solvent.
- Fig. 4 shows 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn * (H)Lu(p-CI)CI] 2. * denotes residual protio solvent.
- Fig. 5 shows 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*Y(p-OAr Me )(thf)] 2 . * denotes residual protio solvent.
- Fig. 6 shows 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*(H)Y(p-OAr tBu )(OAr tBu )] 2 * denotes residual protio solvent.
- Fig. 11 shows temperature variation in the polymerisation of L-lactide using [Pn*Y(p-CI)(thf)] 2 .
- Fig. 12 shows the polymerisation of L- and rac-lactide using [Pn*Y(p-OAr Me )(thf)] 2 in thf-cfe or benzene-cfe.
- Fig. 13 shows homodecoupled 1 H ⁇ 1 H ⁇ studies of L- and rac- lactide polymerised using [Rh*U(m- OAr Me )(thf)] 2 and [Pn*Y(p-CI)(thf)] 2 .
- Fig. 14 shows the 13 C ⁇ 1 H ⁇ NMR spectra of poly(e-caprolactone) synthesised using [Rh * U(m- OAr Me )(thf)] 2 .
- MALDI-ToF-MS were collected using a Voyager DE-STR from Applied Biosystems equipped with a 337 nm nitrogen laser. All other reagents were purchased and used without further purification. Polymer molecular weights were determined by GPC using a Polymer Laboratories Plgel Mixed-D column (300 mm length, 7.5 mm diameter) and a Polymer Laboratories PL-GPC50 Plus instrument equipped with a refractive index detector. L- and rac-lactide was recrystallised twice from toluene and sublimed (70 °C, 103 mbar).
- Fig. 1 shows the 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*Y(p-CI)(thf)] 2 .
- Fig. 2 shows the 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*Lu(p-CI)(thf)] 2 .
- the 1 H NMR spectra of both complexes show two singlets in a ratio of 12H:6H corresponding to the non- wing-tip and wing-tip methyl group protons respectively.
- Fig. 3 shows the 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*(H)Y(p-CI)CI] 2 .
- FIG. 5 shows the 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*Y(p-OAr Me )(thf)] 2 .
- the 1 H NMR spectrum of [Pn*Y(p-OAr Me )(thf)] 2 contains two singlets at 1.78 and 1.86 ppm for the permethylpentalene resonances, a singlet at 2.13 ppm for the aryloxide methyl groups. Two multiplets close to the thf-cfe solvent resonances indicate bound thf.
- Fig. 7 shows the polymerisation of lactide with [Pn * Y(p-CI)(thf)] 2 in two solvent mixtures, as well as with the addition of benzyl alcohol. It is noticeable that when the alcohol is added, the polymerisation is much faster due to the presence of the alkoxide active centre. The change of rate when benzene-cfe is added show that the thf-cfe has a retarding effect on the polymerisation; perhaps due to competition with the active centre.
- Fig. 8 follows on from the findings outlined in Fig. 7 and shows that the alkoxide complex ([Pn*Y(p-OAr Me )(thf)] 2 ) demonstrated a much higher rate of lactide polymerisation than the halide complex ([Pn*Y(p-CI)(thf)] 2 ).
- Fig. 8 shows that the alkoxide complex had consumed all of the available lactide within 1 hour.
- Fig. 8 also shows that the alkoxide complex is extremely active even at room temperature.
- Fig. 9 shows that [Pn*Y(p-CI)(thf)] 2 is more catalytically active in lactide polymerisation at elevated temperatures.
- Fig. 10 compares the catalytic activity of [Pn*Y(p-OAr Me )(thf)] 2 in the polymerisation of lactide with various other permethylpentalene-based complexes known to polymerise lactide.
- Fig. 10 shows that the rare earth-based [Pn*Y(p-OAr Me )(thf)] 2 is significantly more active than the zirconium-based comparators.
- Fig. 11 shows that the rate of polymerisation of L-lactide at room temperature is very slow when [Pn*Y(p-CI)(thf)] 2 was used. However, there is a huge rate increase between 65 and 80°C, certainly due to a high barrier of activation.
- Fig. 12 shows that [Pn * Y(p-OAr Me )thf] 2 is extremely fast at room temperature; too fast to properly monitor. There is little variation in rates between rac- and L-lactide and thf does not significantly slow down the polymerisation.
- Fig. 13 shows NMR spectra highlighting heterotactic biased (>85%) PLA obtained using [Pn*Y(p-CI)(thf)] 2 .
- Atactic biased PLA were obtained for polymerisation of rac-lactide using [Pn*Y(p-OAr Me )thf] 2 .
- Isotactic PLA was obtained from L-lactide using [Pn*Y(p-OAr Me )thf] 2 , demonstrating no epimerisation.
- Fig. 14 shows the 13 C ⁇ 1 H ⁇ NMR spectra highlighting instant polymerisation of e- caprolactone at room temperature using [Pn*Y(p-OAr Me )thf] 2 . Gel formation after less than 2 minutes demonstrates full conversion and extremely active initiators.
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Abstract
A catalytic process for the polymerisation of cyclic ester and cyclic amides is described, which uses, as catalysts, Rare-earth complexes comprising permethylpentalene or (hydro)permethylpentalene ligands. The complexes are notably more active in lactide polymerisation that zirconium-containing analogues.
Description
POLYMERISATION OF CYCLIC ESTERS AND CYCLIC AMIDES
INTRODUCTION
[0001] The present invention relates to a catalytic process for the ring opening polymerisation (ROP) of a cyclic ester or a cyclic amide. More particularly, the catalytic process employs, as catalysts, rare earth metal complexes having permethylpentalene or (hydro)permethylpentalene ligands.
BACKGROUND OF THE INVENTION
[0002] Poly(lactic acids) (PLAs) have been studied intensively over the past few decades due to the promise they have shown as potential alternatives to petroleum-based polymers for uses a plastics, fibres and coatings. Moreover, since PLAs are both biodegradable and biocompatible, they are of equal value to the field of medicine, wherein their versatile physical properties make them suitable for in vivo applications (e.g. as media for controlled drug delivery devices).
[0003] Lactic acid forms PLA upon polycondensation. However, the fact that this reaction is in equilibrium, and the difficulties in completely removing water, makes it difficult to obtain PLAs of high molecular weight. With this in mind, ring opening polymerisation (ROP) of lactides is the most efficient route to PLAs with controlled molecular weights and narrow molecular weight distributions.
[0004] Metal complexes useful for initiating ring opening polymerisation of lactides are known.
[0005] Wenshan Ren et al, Inorganic Chemistry Communications, 30, (2013), 26-28 report that benzyl thorium metallocenes [n5-1 ,3-(Me3C)2CsH3]2 Th(CH2Ph)2 (1) and [n5-1 ,2,4-(Me3C)3CsH2]2 Th(CH2Ph)2 (2) can initiate the ring opening polymerisation of racemic-lactide (rac-LA) under mild conditions. Complete conversion of 500 equiv of lactide occurs within 5h at 40°C in dichloromethane at [rac-LA]=1.0 mol L 1 , and the molecular weight distribution is very narrow (ca.1.15) over the entire monomer-to-initiator range, indicating a single-site catalyst system.
[0006] Yalan Ning et al, Organometallics 2008, 27, 5632-5640 report four neutral zirconocene bis(ester enolate) and non-zirconocene bis(alkoxy) complexes employed for ring-opening polymerisations and chain transfer polymerisations of L-lactide ( -LA) and e- cap ro lactone (e- CL).
[0007] In spite of the above, due to the high value that industry places on such materials, there remains a need for catalysts/initiators capable of effectively polymerising cyclic esters (such as lactides) and cyclic amides.
[0008] The present invention was devised with the foregoing in mind.
SUMMARY OF THE INVENTION
[0009] According to a first aspect of the present invention there is provided a process for the ring opening polymerisation (ROP) of a cyclic ester or a cyclic amide, the process comprising the step of contacting a compound having a structure according to formula (I) defined herein with one or more cyclic esters or cyclic amides.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
[0010] The term“alkyl” as used herein refers to a straight or branched chain alkyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms. This term includes reference to groups such as methyl, ethyl, propyl (n-propyl or isopropyl), butyl (n-butyl, sec-butyl or tert-butyl), pentyl, hexyl and the like. In particular, an alkyl may have 1 , 2, 3 or 4 carbon atoms.
[0011] The term“alkenyl” as used herein refers to straight or branched chain alkenyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms. The term includes reference to alkenyl moieties containing 1 , 2 or 3 carbon-carbon double bonds (C=C). This term includes reference to groups such as ethenyl (vinyl), propenyl (allyl), butenyl, pentenyl and hexenyl, as well as both the cis and trans isomers thereof.
[0012] The term“alkynyl” as used herein refers to straight or branched chain alkynyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms. The term includes reference to alkynyl moieties containing 1 , 2 or 3 carbon-carbon triple bonds (CºC). This term includes reference to groups such as ethynyl, propynyl, butynyl, pentynyl and hexynyl.
[0013] The term“alkoxy” as used herein refers to -O-alkyl, wherein alkyl is straight or branched chain and comprises 1 , 2, 3, 4, 5 or 6 carbon atoms. In one class of embodiments, alkoxy has 1 , 2, 3 or 4 carbon atoms. This term includes reference to groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, hexoxy and the like.
[0014] The term "aryl" as used herein refers to an aromatic ring system comprising 6, 7, 8, 9 or 10 ring carbon atoms. Aryl is often phenyl but may be a polycyclic ring system, having two or
more rings, at least one of which is aromatic. This term includes reference to groups such as phenyl, naphthyl and the like.
[0015] The term “aryloxy” as used herein refers to -O-aryl, wherein aryl has any of the definitions discussed herein. Also encompassed by this term are aryloxy groups in having an alkylene chain situated between the O and aryl groups..
[0016] The term "halogen" or“halo” as used herein refers to F, Cl, Br or I. In a particular, halogen may be F or Cl, of which Cl is more common.
[0017] The term“substituted” as used herein in reference to a moiety means that one or more, especially up to 5, more especially 1 , 2 or 3, of the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of the described substituents. The term“optionally substituted” as used herein means substituted or unsubstituted.
[0018] It will, of course, be understood that substituents are only at positions where they are chemically possible, the person skilled in the art being able to decide (either experimentally or theoretically) without inappropriate effort whether a particular substitution is possible. For example, amino or hydroxy groups with free hydrogen may be unstable if bound to carbon atoms with unsaturated (e.g. olefinic) bonds. Additionally, it will of course be understood that the substituents described herein may themselves be substituted by any substituent, subject to the aforementioned restriction to appropriate substitutions as recognised by the skilled person.
[0019] The terms “cyclic esters” and “cyclic amides” as used herein refer to heterocycles containing at least one ester or amide moiety. It will be understood that lactides, lactones and lactams are encompassed by these terms.
Processes of the invention
[0020] The first aspect of the invention provides a process for the ring opening polymerisation (ROP) of a cyclic ester or a cyclic amide, the process comprising the step of contacting a compound having a structure according to formula (I) shown below with one or more cyclic esters or cyclic amides:
wherein
M1 and M2 are each independently a group 3 metal or a lanthanide,
X1 is selected from halo, (1 -6C)alkoxy, aryl(1 -3C)alkoxy and aryloxy, wherein the (1 -6C)alkoxy, aryl(1 -3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1 -5C)alkyl, (2-5C)alkenyl, (2-5C)alkynyl and (1-5C)alkoxy,
X2 is absent, or is selected from halo, (1 -6C)alkoxy, aryl(1 -3C)alkoxy and aryloxy, wherein the (1 -6C)alkoxy, aryl(1 -3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-5C)alkyl, (2- 5C)alkenyl, (2-5C)alkynyl and (1-5C)alkoxy,
or X2 is a neutral ligand (e.g. a complexed solvent), and
Li and l_2 are each independently selected from permethylpentalene and (hydro)permethylpentalene.
[0021] When compared with existing permethylpentalene-based catalysts for the polymerisation of polar monomers, the compounds of formula (I) are noticeably more active. In particular, the rare earth metal complexes of formula (I) exhibit a stark increase in catalytic activity over zirconium-based analogues.
[0022] M1 and M2 may be independently selected from any group 3 metal or any lanthanide. It will be understood that the compounds of formula (I) are neutral (i.e. they carry no net charge). Therefore, M1 and M2 must each have a complete coordination sphere of charge balancing ligands X1 , X2, L1 and L2.
[0023] In an embodiment, M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium. Suitably, M1 and M2 are each independently selected from yttrium and lutetium.
[0024] In an embodiment, M1 and M2 are the same. Suitably, M1 and M2 are both yttrium or lutetium.
[0025] In an embodiment, X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy.
[0026] It will be understood that X1 may associated with M1 and M2 via electrostatic interactions, or by a mixture of covalent and electrostatic interactions, all of which are shown herein, for simplicity, as solid bonds. When X1 is halo, it associates with M1 and M2 as depicted below:
When X1 is an oxygen-containing ligand, it associates with M1 and M2 as depicted below:
[0027] In an embodiment, X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy.
[0028] In an embodiment, X1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1-4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy.
[0029] In an embodiment, X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1-4C)alkoxy.
[0030] In an embodiment, X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl.
[0031] In an embodiment, X1 v selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl.
[0032] In an embodiment, X1 is selected from chloro, benzyloxy, -0-2,6-dimethyl-phenoxy, -O- 2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy.
[0033] In an embodiment, X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent or another neutral ligand capable of completing the coordination sphere around M1/M2.
[0034] In an embodiment, X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent.
[0035] In an embodiment, X2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1-4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent.
[0036] In an embodiment, X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent.
[0037] In an embodiment, X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent.
[0038] In an embodiment, X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent.
[0039] In an embodiment, X2 is selected from chloro, benzyloxy, -0-2,6-dimethyl-phenoxy, -O- 2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy, or X2 is a complexed solvent.
[0040] In those instances where X2 is a solvent or another neutral ligand capable of completing the coordination sphere around M1/M2, it is suitably selected from an ether or pyridine. It will be understood that the solvent bonding is likely to proceed via an electrostatic interaction (rather than a covalent interaction) between the heteroatom of the solvent and MVM2) via its heteroatom). More suitably, when X2 is a complexed solvent, it is tetrahydrofuran.
[0041] It will be appreciated that in the compounds of formula (I), any of those definitions recited in respect of X1 may be taken in combination with any of those definitions recited in respect of X2.
[0042] U and L2 are independently selected from permethylpentalene and (hydro)permethylpentalene.
[0043] Permethylpentalene (also denoted herein as Pn*) will be understood to refer to the following moiety:
When L1 is permethylpentalene, it typically coordinates to M1 via 2 h5 bonds. Similarly, when L2 is permethylpentalene, it typically coordinates to M2 via 2 h5 bonds. When U/L2 is permethylpentalene, X2 is suitably a complexed solvent or another neutral ligand capable of completing the coordination sphere around MVM2. Alternatively, When U/L2 is permethylpentalene, X2 is absent.
[0044] (Hydro)permethylpentalene (also denoted herein as Pn*(H)) will be understood to refer to the following moiety:
When L1 is (hydro)permethylpentalene, it typically coordinates to M1 via 1 h5 bond. Similarly, when L2 is (hydro)permethylpentalene, it typically coordinates to M2 via 1 h5 bond.
[0045] It will be understood that in the compounds of formula (I), M1, M2, X1 , X2, L1 and L2 may have any of the definitions recited hereinbefore.
[0046] In an embodiment, the compound of formula (I) has a structure according to formula (la) shown below:
wherein M1 , M2, X1 and X2 have any of those definitions recited hereinbefore.
[0047] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0048] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from yttrium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0049] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
X2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0050] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0051] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0052] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy, -0-2,6-dimethyl-phenoxy, -0-2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0053] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0054] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1- 4C)alkoxy; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0055] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0056] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0057] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, benzyloxy, -0-2,6-dimethyl-phenoxy, -0-2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0058] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0059] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0060] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0061] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1- 4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0062] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0063] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0064] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from yttrium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0065] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from yttrium and lutetium;
X1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0066] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from yttrium and lutetium;
X1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1- 4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0067] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from yttrium and lutetium;
X1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0068] In an embodiment, the compound of formula (I) has a structure according to formula (la), wherein
M1 and M2 are each independently selected from yttrium and lutetium;
X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0069] In an embodiment, the compound of formula (I) has a structure according to formula (lb) shown below:
wherein M1 , M2, X1 and X2 have any of those definitions recited hereinbefore.
[0070] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0071] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from yttrium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0072] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
X2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0073] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0074] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0075] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy, -0-2,6-dimethyl-phenoxy, -0-2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0076] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0077] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1- 4C)alkoxy; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0078] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0079] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0080] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, benzyloxy, -0-2,6-dimethyl-phenoxy, -0-2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy; and
X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0081] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0082] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0083] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0084] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1- 4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0085] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0086] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from scandium, yttrium, lanthanum, cerium and lutetium;
X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0087] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from yttrium and lutetium;
X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0088] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from yttrium and lutetium;
X1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0089] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from yttrium and lutetium;
X1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1- 4C)alkoxy, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0090] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from yttrium and lutetium;
X1 is selected from chloro, bromo, (1-4C)alkoxy, benzyloxy and phenoxy, wherein the (1- 4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0091] In an embodiment, the compound of formula (I) has a structure according to formula (lb), wherein
M1 and M2 are each independently selected from yttrium and lutetium;
X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl; and
X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent (e.g. pyridine or tetrahydrofuran).
[0092] In a particularly suitable embodiment, the compound of formula (I) has any one of the following structures:
Ar = 2.6-dirr ethyl-phenyl Ar = 2,4-ditertbutylphenyl
or benzyloxy
[0093] In an embodiment, the one or more cyclic esters or cyclic amides has a structure according to formula (II) shown below
Q is selected from O or NRy, wherein Ry is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl and (2-6C)alkynyl; and
ring A is a 4-23 membered heterocycle containing 1 to 4 O or N ring heteroatoms in total, wherein the heterocycle is optionally substituted with one or more substituents selected from oxo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl and heteroaryl.
[0094] In an embodiment, Q is selected from O or NRy, wherein Ry is selected from hydrogen, (1-3C)alkyl, (2-3C)alkenyl or (2-3C)alkynyl.
[0095] In an embodiment, Q is O.
[0096] In an embodiment, ring A is a 4-18 membered heterocycle containing 1 to 3 O or N ring heteroatoms in total, wherein the heterocycle is optionally substituted with one or more substituents selected from oxo, (1-6C)alkyl, (1-6C)alkoxy and aryl.
[0097] In an embodiment, ring A is a 4-, 6-, 7- or 16-membered heterocycle containing 1 to 3 O or N ring heteroatoms in total, wherein the heterocycle is optionally substituted with one or more substituents selected from oxo, (1-6C)alkyl, (1-6C)alkoxy and aryl.
[0098] In an embodiment, ring A does not contain any N ring heteroatoms.
[0099] In an embodiment, the cyclic ester or cyclic amide is a lactone.
[00100] In an embodiment, the cyclic ester or cyclic amide is a lactam.
[00101] In a particular embodiment, the cyclic ester or cyclic amide is a lactide (e.g. the cyclic diester of 2-hydroxypropionoic acid).
[00102] In an embodiment, the mole ratio of the compound of formula (I) to the cyclic ester or cyclic amide is 1 :5 to 1 :10,000. Suitably, the mole ratio of the compound of formula (I) to the cyclic ester or cyclic amide is 1 :10 to 1 : 1000. More suitably, the mole ratio of the compound of formula (I) to the cyclic ester or cyclic amide is 1 :25 to 1 :250.
[00103] In an embodiment, the process is not conducted in a solvent.
[00104] In an embodiment, the process is conducted in a solvent selected from toluene, tetrahydrofuran and methylene chloride.
[00105] In an embodiment, the process is conducted for a period of 1 minute to 96 hours. Suitably, the process is conducted for a period of 5 minute to 72 hours.
[00106] In an embodiment, the process is conducted at a pressure of 0.9 to 5 bar. Suitably, the process is conducted at a pressure of 0.9 to 2 bar.
[00107] In an embodiment, the process is conducted at a temperature of 10 - 150°C. Suitably, the process is conducted at a temperature ³50°C (e.g. 50 - 150°C. More suitably, the process is conducted at a temperature greater than ³60°C (e.g. 60 - 150°C). Most suitably, the process is conducted at a temperature greater than ³70°C (e.g. 70 - 150°C or 70 - 120°C).
[00108] In an embodiment, the process is conducted in the presence of a chain transfer agent suitable for use in the ring opening polymerisation of a cyclic ester or cyclic amide. Suitably, the chain transfer agent is a hydroxy-functional compound (e.g. an alcohol, diol or polyol). More suitably, the chain transfer agent is selected from the group consisting of tert-butanol, benzyl alcohol and iso-propanol.
Preparation of compounds of formula (I)
[00109] The compounds of formula (I) may be formed by any suitable process known in the art. Particular examples of processes for the preparing compounds for formula (I) are set out in the accompanying examples.
[00110] Generally, when U and L2 are permethylpentalene (Pn*), the process of preparing a compound of formula (I) comprises:
i. reacting [U2(tmeda)][Pn*] (tmeda = tetramethylethylenediamine), shown below
©
Ma(X)3
(A) wherein
Ma has any of the identities discussed herein in relation to M1 or M2, and
X is a halide (e.g. chloro); and
ii. optionally reacting the product of step i with a compound of formula (B) shown below:
MbR
(B) wherein
Mb is an alkali metal (e.g. potassium), and
R is (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1- 3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-5C)alkyl, (2-5C)alkenyl, (2-5C)alkynyl and (1- 5C)alkoxy.
[00111] Generally, when L1 and L2 are (hydro)permethylpentalene (Pn*(H)), the process of preparing a compound of formula (I) comprises:
i. reacting LiPn*(H), shown below
Ma(X)3
(A) wherein
Ma has any of the identities discussed herein in relation to M1 or M2, and
X is a halide (e.g. chloro); and
ii. optionally reacting the product of step i with a compound of formula (B) shown below:
MbR
(B) wherein
Mb is an alkali metal (e.g. potassium), and
R is (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1- 3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-5C)alkyl, (2-5C)alkenyl, (2-5C)alkynyl and (1- 5C)alkoxy.
[00112] It will be appreciated that when X1 (and, optionally X2) is halo, step ii need not be carried out.
[00113] It will be appreciated that any suitable solvent may be used in steps i and ii. Depending on the nature of X1, L1 and L2, the solvent used in step i and/or step ii may complex to M1/M2 as neutral ligand, X2. Suitably, the solvent used in steps i and ii is tetrahydrofuran.
[00114] A person of skill in the art will be able to select suitable reaction conditions (e.g. temperature, pressures, reaction times, agitation etc.) for syntheses.
EXAMPLES
[00115] One or more examples of the invention will now be described, for the purpose of illustration only, with reference to the accompanying figures, in which:
Fig. 1 shows 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*Y(p-CI)(thf)]2. * denotes residual protio solvent and bound thf, and + denotes residual tmeda.
Fig. 2 shows 1H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*Lu(p-CI)(thf)]2. * denotes residual protio solvent and bound thf, and + denotes residual tmeda.
Fig. 3 shows 1H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*(H)Y(p-CI)CI]2. * denotes residual protio solvent.
Fig. 4 shows 1H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*(H)Lu(p-CI)CI]2. * denotes residual protio solvent.
Fig. 5 shows 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*Y(p-OArMe)(thf)]2. * denotes residual protio solvent.
Fig. 6 shows 1H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*(H)Y(p-OArtBu)(OArtBu)]2 * denotes residual protio solvent.
Fig. 7 shows the polymerisation of of -lactide using [Pn*Y(p-CI)(thf)]2 at 80 °C with [LA]0 = 0.5 M, [LA]o/[Y]o = 50 in thf-cfe (black square), in benzene-Gf6/thf-cf8 (black circle) and with two equivalents of benzyl alcohol in benzene-cf6/thf-cf8 (black triangle).
Fig. 8 shows the polymerisation of -lactide at 23 °C with [LA]0 = 0.5 M, [LA]o/[Y]o = 50 in benzene-Gf6/thf-cf8 using [Pn*Y(p-CI)(thf)]2 (black diamond) and [Pn*Y(p-OArMe)(thf)]2 (black circle).
Fig. 9 shows the polymerisation of L-lactide using [Pn*Y(p-CI)(thf)]2with [LA]o = 0.5 M, [LA]o/[Y]o = 50 in benzene- cfe/thf- da at 80 °C (black diamond) and 23 °C (black circle).
Fig. 10 shows the polymerisation of L-lactide at 80 °C with [LA]0 = 0.5 M, [LA]o/[M]0 = 50 in benzene-cfe/thf-cfe using [Pn*Y(p-OArMe)(thf)]2 (black circle), Pn*Zr(0-2,6-Me-C6H3)2 (black square), Pn*ZrCp(0-2,6-Me-CsH3) (black triangle) and Pn*ZrCp(0‘Bu) (down triangle).
Fig. 11 shows temperature variation in the polymerisation of L-lactide using [Pn*Y(p-CI)(thf)]2. Polymerisation condition: CeD6, 40 mg of lactide, [LA]0 = 0.5 M and [LA]0/[M]0 = 50.
Fig. 12 shows the polymerisation of L- and rac-lactide using [Pn*Y(p-OArMe)(thf)]2 in thf-cfe or benzene-cfe. Polymerisation condition: 25 °C, 40 mg of lactide, [LA]0 = 0.5 M and [LA]0/[M]0 = 50. 90% conversion correspond to 2.2.
Fig. 13 shows homodecoupled 1H{1 H} studies of L- and rac- lactide polymerised using [Rh*U(m- OArMe)(thf)]2 and [Pn*Y(p-CI)(thf)]2. Polymerisation condition: 40 mg of lactide, [LA]o = 0.5 M and [LA]o/[M]o = 50.
Fig. 14 shows the 13C{1 H} NMR spectra of poly(e-caprolactone) synthesised using [Rh*U(m- OArMe)(thf)]2. Polymerisation condition: 48.5 mg of e-caprolactone, [e-CLJo = 0.5 M and [e- CL]o/[Y]o = 25.
General details
[00116] General Considerations. All manipulations were carried out using standard Schlenk line or drybox techniques under an atmosphere of dinitrogen. Protio solvents were i) (pentane, hexane, toluene, benzene) degassed by sparging with dinitrogen, dried by passing through a column of activated sieves and stored over potassium mirrors ii) (thf, diethyl ether) distilled from sodium metal and stored activated 4 A molecular sieves (thf). Deuterated solvents were dried over potassium (C6D6) or CaH2 (CDCh), distilled under reduced pressure, freeze-pump-thaw degassed three times prior to use. 1H NMR spectra were recorded at 298 K, unless otherwise stated, on Varian Mercury VX-Works 300 or Bruker AVA 500 spectrometers and 13C{1H} or 13C spectra on the same spectrometers at operating frequencies of 75 and 125 MHz respectively. Two dimensional 1 H-1H and 13C-1 H correlation experiments were used, when necessary, to confirm 1 H and 13C assignments. All NMR spectra were referenced internally to residual protio solvent (1H) or solvent (13C) resonances and are reported relative to tetramethylsilane (d = 0 ppm). Chemical shifts are quoted in d (ppm) and coupling constants in Hertz. Elemental analyses were carried out at London Metropolitan University. MALDI-ToF-MS were collected using a Voyager DE-STR from Applied Biosystems equipped with a 337 nm nitrogen laser. All other reagents were purchased and used without further purification. Polymer molecular weights were determined by GPC using a Polymer Laboratories Plgel Mixed-D column (300 mm length, 7.5 mm diameter) and a Polymer Laboratories PL-GPC50 Plus instrument
equipped with a refractive index detector. L- and rac-lactide was recrystallised twice from toluene and sublimed (70 °C, 103 mbar).
[00117] X-ray crystallography. Crystals were mounted on glass fibres using perfluoropolyether oil, transferred to a goniometer head on the diffractometer and cooled rapidly to 150 K. Data collections were performed using an Enraf-Nonius FR590 KappaCCD diffractometer, utilising graphite-monochromated Mo Ka X-ray radiation (l = 0.71073 A). Intensity data were processed using the DENZO-SMN package and corrected for absorption using SORTAV. The structures were solved using direct methods (SIR-92) or a charge flipping algorithm (SUPERFLIP) and refined by full-matrix least-squares procedures.
[00118] Polymerisation procedure. The lactide monomer (40 mg) and the complex were introduced in an NMR tube following the desired monomerinitiator ratio. Then 0.57 mL of chloroform-cfi was added to the compounds, leading to an initial monomer concentration of [LA]0 = 0.5 M. The solution was monitored by 1FI NMR spectroscopy. The conversion was determined by comparing the integration of the methine resonance of the polymer to the monomer.
Example 1 - Synthesis of catalytic complexes
1.1 - Synthesis of permethylpentalene halide complexes
[00119] Flaving regard to Scheme 1 below, reaction of MCh (M = Y or Lu) with [Li2(tmeda)][Pn*] in thf for 30 minutes afforded a yellow-orange solution containing [Rh*M(m- Cl)(thf)]2 in quantitative yield as judged by 1FI NMR spectroscopy.
Scheme 1 : Synthesis of [Pn*M(p-CI)(thf)]2 (M = Y or Lu)
[00120] Fig. 1 shows the 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*Y(p-CI)(thf)]2. Fig. 2 shows the 1H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*Lu(p-CI)(thf)]2. The 1H NMR
spectra of both complexes show two singlets in a ratio of 12H:6H corresponding to the non- wing-tip and wing-tip methyl group protons respectively.
1.2 - Synthesis of (hvdro)permethylpentalene halide complexes
[00121] Having regard to Scheme 2 below, reaction of MCI3 (M = Y or Lu) with LiPn*(H) in thf for 30 minutes afforded yellow-orange [Pn*(H)M(p-CI)CI]2 in quantitative yields. Removal of the volatiles in vacuo and extraction in pentane afforded crystals suitable for a single crystal X-ray diffraction study. Connectivity obtained from the data set showed a [YCl2]n cluster that had both bound THF and Pn*(H)_ ligands. This suggests that the dimeric [Pn*(H)M(p-CI)CI]2 is likely stabilised by coordinating THF when in solution.
Scheme 2: Synthesis of [Pn*(H)M(p-CI)CI]2 (M = Y or Lu)
[00122] Fig. 3 shows the 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*(H)Y(p-CI)CI]2. Fig.
4 shows the 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*(H)Lu(p-CI)CI]2. The 1 H NMR spectra of [Pn*(H)M(p-CI)CI]2 show a quartet at ~3.2 ppm and doublet at ~1.1 ppm which are characteristic of the methine proton and methyl group in the C1 position in Pn*(H)_ complexes.
5 singlets define the remaining methyl groups. Small amounts of other isomers (by virtue of planar chirality) are clearly visible in the NMR spectra but it is clear that a single major isomer is formed under ambient conditions.
1.3 - Synthesis of permethyloentalene aryloxide complexes
[00123] In order to avoid any aggregation during desolvation of the permethylpentalene rare earth halide complexes, these complexes were generated in situ and then reacted with potassium aryloxides in an effort to afford the corresponding aryloxide-substituted complexes. It was expected that the bulky aryloxide ligands would be both solubilising and stabilising.
[00124] Having regard to Scheme 3 below, reaction of [Pn*M(p-CI)(thf)]2 (M = Y or Lu) with 2 equivalents of KOArR derivatives (OArR = 0-2,6-Me-C6H3 or ArMe, 0-2,6-'Pr-C6H3 or OAr'Pr) led to instant consumption of starting materials as judged by 1 H NMR spectroscopy and products consistent with the desired aryloxide complexes [Pn*M(p-OAr)(thf)]2.
Scheme 3: Synthesis of [Pn*M(p-OArR)(thf)]2 (M = Y or Lu, OAr = 0-2,6-Me-C6H3 (0ArMe), O-
2,6-'Pr-CsH3 (OAriPr))
[00125] Fig. 5 shows the 1H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Pn*Y(p-OArMe)(thf)]2. The 1H NMR spectrum of [Pn*Y(p-OArMe)(thf)]2 contains two singlets at 1.78 and 1.86 ppm for the permethylpentalene resonances, a singlet at 2.13 ppm for the aryloxide methyl groups. Two multiplets close to the thf-cfe solvent resonances indicate bound thf.
1.4 - Synthesis of (hvdro)permethylpentalene aryloxide complexes
[00126] In order to avoid any aggregation during desolvation of the (hydro)permethylpentalene rare earth halide complexes, these complexes were generated in situ and then reacted with potassium aryloxides in an effort to afford the corresponding aryloxide-substituted complexes. It was expected that the bulky aryloxide ligands would be both solubilising and stabilising.
[00127] Having regard to Scheme 4 below, reaction of [Pn*(H)Y(p-CI)CI]2 with 4 equivalents of KO-2,4-‘Bu-C6H3 afforded a product consistent with [Pn*(H)Y(p-OArtBu)(OArtBu)]2 as judged by 1H NMR spectroscopy.
Scheme 4: Synthesis of [Pn*(H)Y(p-OArtBu)(OArtBu)]2 (OArtBu = 0-2,4-tBu-C6H3).
[00128] Fig. 6 shows the 1 H NMR spectrum (400 MHz, 298 K, thf-cfe) of [Rh*(H)U(m- OArtBu)(OArtBu)]2 (OArtBu = 0-2,4-iBu-06H3).
Example 2 - Polymerisation studies
[00129] The ability of the complexes of Example 1 to catalyse the polymerisation of L-lactide was assessed according to the protocol discussed in the general details.
[00130] Fig. 7 shows the polymerisation of lactide with [Pn*Y(p-CI)(thf)]2 in two solvent mixtures, as well as with the addition of benzyl alcohol. It is noticeable that when the alcohol is added, the polymerisation is much faster due to the presence of the alkoxide active centre. The change of rate when benzene-cfe is added show that the thf-cfe has a retarding effect on the polymerisation; perhaps due to competition with the active centre.
[00131] Fig. 8 follows on from the findings outlined in Fig. 7 and shows that the alkoxide complex ([Pn*Y(p-OArMe)(thf)]2) demonstrated a much higher rate of lactide polymerisation than the halide complex ([Pn*Y(p-CI)(thf)]2). In particular, Fig. 8 shows that the alkoxide complex had consumed all of the available lactide within 1 hour. Fig. 8 also shows that the alkoxide complex is extremely active even at room temperature.
[00132] Fig. 9 shows that [Pn*Y(p-CI)(thf)]2 is more catalytically active in lactide polymerisation at elevated temperatures.
[00133] Fig. 10 compares the catalytic activity of [Pn*Y(p-OArMe)(thf)]2in the polymerisation of lactide with various other permethylpentalene-based complexes known to polymerise lactide. Fig. 10 shows that the rare earth-based [Pn*Y(p-OArMe)(thf)]2is significantly more active than the zirconium-based comparators.
[00134] Fig. 11 shows that the rate of polymerisation of L-lactide at room temperature is very slow when [Pn*Y(p-CI)(thf)]2 was used. However, there is a huge rate increase between 65 and 80°C, certainly due to a high barrier of activation.
[00135] Fig. 12 shows that [Pn*Y(p-OArMe)thf]2 is extremely fast at room temperature; too fast to properly monitor. There is little variation in rates between rac- and L-lactide and thf does not significantly slow down the polymerisation.
[00136] Fig. 13 shows NMR spectra highlighting heterotactic biased (>85%) PLA obtained using [Pn*Y(p-CI)(thf)]2. Atactic biased PLA were obtained for polymerisation of rac-lactide using [Pn*Y(p-OArMe)thf]2. Isotactic PLA was obtained from L-lactide using [Pn*Y(p-OArMe)thf]2, demonstrating no epimerisation.
[00137] Fig. 14 shows the 13C{1 H} NMR spectra highlighting instant polymerisation of e- caprolactone at room temperature using [Pn*Y(p-OArMe)thf]2. Gel formation after less than 2 minutes demonstrates full conversion and extremely active initiators.
[00138] While specific embodiments of the invention have been described herein for the purpose of reference and illustration, various modifications will be apparent to a person skilled in the art without departing from the scope of the invention as defined by the appended claims.
Claims
1. A process for the ring opening polymerisation (ROP) of a cyclic ester or a cyclic amide, the process comprising the step of contacting a compound having a structure according to formula (I) shown below with one or more cyclic esters or cyclic amides:
M1 and M2 are each independently a group 3 metal or a lanthanide,
X1 is selected from halo, (1 -6C)alkoxy, aryl(1 -3C)alkoxy and aryloxy, wherein the (1 -6C)alkoxy, aryl(1 -3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1 -5C)alkyl, (2-5C)alkenyl, (2-5C)alkynyl and (1-5C)alkoxy,
X2 is absent, or is selected from halo, (1 -6C)alkoxy, aryl(1 -3C)alkoxy and aryloxy, wherein the (1 -6C)alkoxy, aryl(1 -3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-5C)alkyl, (2- 5C)alkenyl, (2-5C)alkynyl and (1-5C)alkoxy,
or X2 is a neutral ligand (e.g. a complexed solvent), and
Li and Lå are each independently selected from permethylpentalene and (hydro)permethylpentalene.
2. The process of claim 1 , wherein M1 and M2 are each independently selected from
scandium, yttrium, lanthanum, cerium and lutetium.
3. The process of claim 1 or 2, wherein M1 and M2 are each independently selected from yttrium and lutetium
4. The process of claim 1 , 2 or 3, wherein X1 is selected from halo, (1-6C)alkoxy, aryl(1- 3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups
may be optionally substituted with one or more substituents selected from halo, (1- 4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy.
5. The process of any preceding claim, wherein X1 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy.
6. The process of any preceding claim, wherein X1 is selected from chloro, bromo, (1- 4C)alkoxy, benzyloxy and phenoxy, wherein the (1-4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy.
7. The process of any preceding claim, wherein X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1-4C)alkoxy.
8. The process of any preceding claim, wherein X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl.
9. The process of any preceding claim, wherein X1 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl.
10. The process of any preceding claim, wherein X1 is selected from chloro, benzyloxy, -O- 2,6-dimethyl-phenoxy, -0-2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy.
11. The process of any preceding claim, wherein X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy, or X2 is a complexed solvent.
12. The process of any preceding claim, wherein X2 is selected from halo, (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy, wherein the (1-6C)alkoxy, aryl(1-3C)alkoxy and aryloxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent.
13. The process of any preceding claim, wherein X2 is selected from chloro, bromo, (1- 4C)alkoxy, benzyloxy and phenoxy, wherein the (1-4C)alkoxy, benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from halo, (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent.
14. The process of any preceding claim, wherein X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from (1-4C)alkyl and (1-4C)alkoxy, or X2 is a complexed solvent.
15. The process of any preceding claim, wherein X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with one or more substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent.
16. The process of any preceding claim, wherein X2 is selected from chloro, benzyloxy and phenoxy, wherein the benzyloxy and phenoxy groups may be optionally substituted with two substituents selected from methyl, isopropyl and tertbutyl, or X2 is a complexed solvent.
17. The process of any preceding claim, wherein X2 is selected from chloro, benzyloxy, -O- 2,6-dimethyl-phenoxy, -0-2,6-diisopropyl-phenoxy and -0-2,4-ditertbutyl-phenoxy, or X2 is a complexed solvent.
18. The process of any preceding claim, wherein when X2 is a complexed solvent, it is selected from ether and pyridine.
19. The process of claim 18, wherein the ether is tetrahydrofuran.
20. The process of any preceding claim, wherein X1 and X2 have the same identity.
21. The process of any preceding claim, wherein and l_2 are both permethylpentalene, such that the compound of formula (I) has a structure according to formula (la) shown below:
22. The process of any one of claims 1 to 20, wherein and l_2 are both
(hydro)permethylpentalene, such that the compound of formula (I) has a structure according to formula (lb) shown below:
23. The process of claim 1 , wherein the compound has any one of the following structures:
24. The process of any preceding claim, wherein the one or more cyclic esters or cyclic amides has a structure according to formula (II) shown below:
Q is selected from O or NRy, wherein Ry is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl and (2-6C)alkynyl; and
ring A is a 4-23 membered heterocycle containing 1 to 4 O or N ring heteroatoms in total, wherein the heterocycle is optionally substituted with one or more substituents selected from oxo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl and heteroaryl.
25. The process of claim 24, wherein Q is selected from O or NRy, wherein Ry is selected from hydrogen, (1-3C)alkyl, (2-3C)alkenyl or (2-3C)alkynyl.
26. The process of claim 24 or 25, wherein Q is O.
27. The process of claim 24, 25 or 26, wherein ring A is a 4-18 membered heterocycle containing 1 to 3 O or N ring heteroatoms in total, wherein the heterocycle is optionally substituted with one or more substituents selected from oxo, (1-6C)alkyl, (1-6C)alkoxy and aryl.
28. The process of any one of claims 24 to 27, wherein ring A is a 4-, 6-, 7- or 16- membered heterocycle containing 1 to 3 O or N ring heteroatoms in total, wherein the heterocycle is optionally substituted with one or more substituents selected from oxo,
(1 -6C)alkyl, (1-6C)alkoxy and aryl.
29. The process of any one of claims 24 to 28, wherein ring A does not contain any N ring heteroatoms.
30. The process of any one of claims 24 to 29, wherein the cyclic ester or cyclic amide is a lactone.
31. The process of any one of claims 24 to 29, wherein the cyclic ester or cyclic amide is a lactide.
32. The process of any one of claims 24 to 28, wherein the cyclic ester or cyclic amide is a lactam.
33. The process of any one of claims 24 to 32, wherein the mole ratio of the compound of formula (I) to the cyclic ester or cyclic amide is 1 :5 to 1 : 10,000.
34. The process of any one of claims 24 to 33, wherein the mole ratio of the compound of formula (I) to the cyclic ester or cyclic amide is 1 : 10 to 1 : 1000.
35. The process of any one of claims 24 to 34, wherein the mole ratio of the compound of formula (I) to the cyclic ester or cyclic amide is 1 :25 to 1 :250
36. The process of any one of claims 24 to 35, wherein the process is not conducted in a solvent.
37. The process of any one of claims 24 to 35, wherein the process is conducted in a solvent selected from toluene, tetrahydrofuran and methylene chloride.
38. The process of any one of claims 24 to 37, wherein the process is conducted for a period of 1 minute to 96 hours.
39. The process of any one of claims 24 to 38, wherein the process is conducted for a period of 5 minute to 72 hours.
40. The process of any one of claims 24 to 39, wherein the process is conducted at a
pressure of 0.9 to 5 bar.
41. The process of any one of claims 24 to 40, wherein the process is conducted at a
pressure of 0.9 to 2 bar.
42. The process of any one of claims 24 to 41 , wherein the process is conducted at a
temperature of 10 - 150°C.
43. The process of any one of claims 24 to 42, wherein the process is conducted in the presence of a chain transfer agent suitable for use in the ring opening polymerisation of a cyclic ester or cyclic amide.
44. The process of claim 43, wherein the chain transfer agent is a hydroxy-functional
compound (e.g. an alcohol, diol or polyol).
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2134668A2 (en) * | 2007-03-09 | 2009-12-23 | ISIS Innovation Limited | Pentalenes |
EP3129389A2 (en) * | 2014-04-09 | 2017-02-15 | SCG Chemicals Co., Ltd. | Group ivb transition metal catalyst containing at least one cp ring as polymerization catalyst for lactide polymers |
WO2017060691A1 (en) * | 2015-10-06 | 2017-04-13 | Scg Chemicals Co., Ltd. | Use of compounds in polymerisation reactions |
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2017
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EP2134668A2 (en) * | 2007-03-09 | 2009-12-23 | ISIS Innovation Limited | Pentalenes |
EP3129389A2 (en) * | 2014-04-09 | 2017-02-15 | SCG Chemicals Co., Ltd. | Group ivb transition metal catalyst containing at least one cp ring as polymerization catalyst for lactide polymers |
WO2017060691A1 (en) * | 2015-10-06 | 2017-04-13 | Scg Chemicals Co., Ltd. | Use of compounds in polymerisation reactions |
Non-Patent Citations (2)
Title |
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F. MARK CHADWICK ET AL: "Early Transition Metal Permethylpentalene Complexes for the Polymerization of Ethylene", ORGANOMETALLICS, vol. 33, no. 14, 28 July 2014 (2014-07-28), US, pages 3775 - 3785, XP055325337, ISSN: 0276-7333, DOI: 10.1021/om5004754 * |
SUMMERSCALES O T ET AL: "The organometallic chemistry of pentalene", COORDINATION CHEMISTRY REVIEWS, ELSEVIER SCIENCE, AMSTERDAM, NL, vol. 250, no. 9-10, 10 January 2006 (2006-01-10), pages 1122 - 1140, XP028025580, ISSN: 0010-8545, [retrieved on 20060501], DOI: 10.1016/J.CCR.2005.11.020 * |
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