RU2326123C2 - Catalyst system - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: catalyst system is described. It consists of compounds with general formula I

or its salt, bonded to a VIIIB metal, where A₁ and A₂, as well as A₃, A₄ and A₅ (when present), K, D, E, X¹-X⁴, Q¹, Q², M, L¹ assume values given in the formula of invention.

EFFECT: system is suitable for carbonylation of ethenoid unsaturated compounds.

45 cl, 32 ex, 9 tbl

Description

This invention relates to compounds, in particular compounds for catalysis of the carbonylation reaction of ethylene unsaturated compounds, methods for producing such compounds and the use of such compounds for catalysis of the carbonylation reaction of ethylene unsaturated compounds.

Carbonylation of ethylenically unsaturated compounds using carbon monoxide in the presence of a catalyst system and alcohol or water to form the corresponding ester or carboxylic acid, respectively, is well known. Suitable catalyst systems include a Group VIII metal (e.g., palladium) and a phosphine ligand (e.g., an alkylphosphine or a bidentate phosphine ligand, as disclosed in WO-A-9619434).

Although catalyst systems have been developed that exhibit suitable stability during the carbonylation reaction and achieve relatively high reaction rates, there is still a need for improved catalyst systems. Therefore, the present invention aims to provide an improved catalyst for the carbonylation reaction of ethylene unsaturated compounds.

According to a first aspect, the invention provides a catalyst suitable for carbonylation of ethylenically unsaturated compounds, which is obtained by combining:

(a) a metal of group VIIIB or a compound thereof; and

(b) a compound of formula I or a salt thereof:

Where:

A ₁ and A ₂ , as well as A ₃ , A ₄ and A ₅ (when present), each independently, are lower alkylene;

K is selected from the group consisting of hydrogen, lower alkyl, aryl, hetero, halogen, cyano, nitro, -OR ¹⁹ , -OC (O) R ²⁰ , -C (O) R ²¹ , -C (O) OR ²² , -N (R ²³ ) R ²⁴ , -C (O) N (R ²⁵ ) R ²⁶ , -C (S) (R ²⁷ ) R ²⁸ , -SR ²⁹ , -C (O) SR ³⁰ , -CF ₃ or -A ₃ -Q ³ (X ⁵ ) X ⁶ ;

D is selected from the group consisting of hydrogen, lower alkyl, aryl, hetero, halogen, cyano, nitro, -OR ¹⁹ , -OC (O) R ²⁰ , -C (O) R ²¹ , -C (O) OR ²² , -N (R ²³ ) R ²⁴ , -C (O) N (R ²⁵ ) R ²⁶ , -C (S) (R ²⁷ ) R ²⁸ , -SR ²⁹ , -C (O) SR ³⁰ , -CF ₃ or -Q ₄ -A ⁴ (X ⁷⁾ X ^8;

E is selected from the group consisting of hydrogen, lower alkyl, aryl, hetero, halogen, cyano, nitro, -OR ¹⁹ , -OC (O) R ²⁰ , -C (O) R ²¹ , -C (O) OR ²² , -N (R ²³ ) R ²⁴ , -C (O) N (R ²⁵ ) R ²⁶ , -C (S) (R ²⁷ ) R ²⁸ , -SR ²⁹ , -C (O) SR ³⁰ , -CF ₃ or -A ₅ -Q ⁵ (X ⁹ ) X ¹⁰ ;

or together D and E, together with the carbon atoms of the cyclopentadienyl ring to which they are attached, form an optionally substituted phenyl ring:

X ¹ represents CR ¹ (R ² ) (R ³ ), congressyl or adamantyl, X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), congressil or adamantyl, or X ¹ and X ² together with Q ² , to which they are attached form an optionally substituted 2-phosphatricyclo [3.3.1.1 {3,7}] decyl group or derivative thereof, or X ¹ and X ² together with Q ² to which they are attached form a cyclic system of formula 1a

X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ), congressyl or adamantyl, X ⁴ represents CR ¹⁰ (R ¹¹ ) (R ¹² ), congressyl or adamantyl, or X ³ and X ⁴ together with Q ¹ , to which they are attached form an optionally substituted 2-phosphatricyclo [3.3.1.1 {3,7}] decyl group or derivative thereof, or X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of formula 1b

X ⁵ is CR ¹³ (R ¹⁴ ) (R ¹⁵ ), congressyl or adamantyl, X ⁶ is CR ¹⁶ (R ¹⁷ ) (R ¹⁸ ), congressyl or adamantyl, or X ⁵ and X ⁶ together with Q ³ , to which they are attached form an optionally substituted 2-phosphatricyclo [3.3.1.1 {3,7}] decyl group or derivative thereof, or X ⁵ and X ⁶ together with Q ³ to which they are attached form a cyclic system of formula 1c

X ⁷ represents CR ³¹ (R ³² ) (R ³³ ), congressyl or adamantyl, X ⁸ represents CR ³⁴ (R ³⁵ ) (R ³⁶ ), congressyl or adamantyl, or X ⁷ and X ⁸ together with Q ⁴ , to which they are attached form an optionally substituted 2-phosphatricyclo [3.3.1.1 {3,7}] decyl group or derivative thereof, or X ⁷ and X ⁸ together with Q ³ to which they are attached form a cyclic system of formula 1d

X ⁹ represents CR ³⁷ (R ³⁸ ) (R ³⁹ ), congressyl or adamantyl, X ¹⁰ represents CR ⁴⁰ (R ⁴¹ ) (R ⁴² ), congressil or adamantyl, or X ⁹ and X ¹⁰ together with Q ⁵ , to which they are attached form an optionally substituted 2-phosphatricyclo [3.3.1.1 {3,7}] decyl group or derivative thereof, or X ⁹ and X ¹⁰ together with Q ⁵ to which they are attached form a cyclic system of formula 1e

Q ¹ and Q ² and Q ^3, Q ⁴ and Q ⁵ (when present) each independently represent phosphorus, arsenic or antimony;

M represents a metal of group VIB or VIIIB or its cation;

L ₁ represents an optionally substituted cyclopentadienyl, indenyl or aryl group;

L ₂ represents one or more ligands, each of which is independently selected from hydrogen, lower alkyl, alkylaryl, halogen, CO, P (R ⁴³ ) (R ⁴⁴ ) R ⁴⁵ or N (R ⁴⁶ ) (R ⁴⁷ ) R ⁴⁸ ;

groups R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, each independently, are hydrogen, lower alkyl, aryl, halogen or hetero;

groups R ¹⁹ to R ³⁰ and R ⁴³ to R ⁴⁸ , when present, each independently, are hydrogen, lower alkyl, aryl or hetero;

R ⁴⁹ , R ⁵⁴ and R ⁵⁵ , when present, are each independently hydrogen, lower alkyl or aryl.

from R ⁵⁰ to R ^53, when present, each independently represent hydrogen, lower alkyl, aryl or hetero;

Y ¹ , Y ² , Y ³ , Y ^4, or Y ⁵ when present, each independently, is oxygen, sulfur, or NR ⁵⁵ ;

n is 0 or 1;

and m = 0 to 5;

moreover, when n = 1, then m is 0, and when n is 0, then m is not 0.

Such compounds are hereinafter referred to as "compounds of the invention."

Preferably in the compound of formula I, when simultaneously K represents -A ₃ -Q ³ (X ⁵ ) X ⁶ and E represents -A ₅ -Q ⁵ (X ⁹ ) X ¹⁰ , then D represents -A ₄ -Q ⁴ (X ⁷ ) X ⁸ .

Suitably, when the compounds of the invention can catalyze the carbonylation of unsaturated compounds, in particular ethylenically unsaturated compounds, in the presence of carbon monoxide and a co-reagent. In particular, the compounds of the invention can be used in hydroformylation, hydrocarboxylation, hydroetherification and hydroamidation reactions. For example, the compounds of the invention can catalyze the conversion of an ethylenically unsaturated compound in the presence of carbon monoxide and a compound containing a hydroxyl group to the corresponding carboxylic acid or ester, respectively, depending on the choice of the used compound containing the hydroxyl group (e.g., carboxylic acid, if the compound containing a hydroxyl group is water, and an ester if the compound containing a hydroxyl group is alcohol).

Conveniently, the compounds of the invention can exhibit high stability under the conditions of a typical carbonylation reaction so that they require less or no replenishment. Conveniently, when the compounds of the invention can increase the carbonylation reaction rate of an ethylenically unsaturated compound in comparison with known catalysts. Conveniently, when the compounds of the invention can increase speeds with high conversion of an ethylenically unsaturated compound, leading to the desired product in high yield with little or no impurities. Conveniently, the use of the compounds of the invention can increase the commercial viability of a carbonylation reaction such as the carbonylation of an ethylenically unsaturated compound. Conveniently, the compounds of the invention typically exhibit high catalytic performance in the carbonylation reaction of an unsaturated compound, in particular an ethylenically unsaturated compound, in the presence of carbon monoxide and a co-reagent, as defined herein.

It was unexpectedly found that if the carbon atoms of X ¹ and X ² bonded to Q ² and the carbon atoms of X ³ and X ⁴ bonded to Q ¹ do not include a hydrogen atom in the compound of formula I, this usually gives a catalyst which exhibits increased catalytic performance in the carbonylation reaction of an unsaturated compound compared to a comparable compound in which the carbon atom present in X ¹ and / or X ² and X ³ and / or X ⁴ bonded to Q ² and Q ^1, respectively, includes in itself a hydrogen atom. Most preferably, if Q ¹ is bonded to a tertiary carbon atom of both X ³ and X ⁴ , and Q ² is bonded to a tertiary carbon atom of both X ¹ and X ² . The carbon atoms from X ⁵ and X ⁶ bonded to Q ³ , from X ⁷ and X ⁸ bonded to Q ⁴ , and from X ⁹ and X ¹⁰ bonded to Q ⁵ also usually, if present, do not include an atom hydrogen. Most preferably, when Q ³ , Q ⁴ and Q ⁵ , if present, are bonded to the tertiary carbon atom of both X ⁵ and X ⁶ , X ⁷ and X ⁸ , X ⁹ and X ¹⁰ , respectively.

Preferably, the groups R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, are each independently hydrogen, optionally substituted C ₁ -C ₆ alkyl, C ₁ -C ₆ alkyl phenyl (in which the phenyl group is optionally substituted, as defined here), trifluoromethyl or phenyl (in which the phenyl group is optionally substituted, as defined here). Even more preferably, groups R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, are each independently hydrogen, C ₁ -C ₆ alkyl, which is optionally substituted, as defined herein, trifluoromethyl or optionally substituted phenyl. Even more preferably, the groups R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, are each independently hydrogen, unsubstituted C ₁ -C ₆ alkyl or phenyl, which is optionally substituted with one or more substituents, selected from unsubstituted C ₁ -C ₆ alkyl or OR ¹⁹ , where R ¹⁹ is hydrogen or unsubstituted C ₁ -C ₆ alkyl. More preferably, groups R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, are each independently hydrogen or unsubstituted C ₁ -C ₆ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n -butyl, isobutyl, tert-butyl, pentyl, hexyl and cyclohexyl, in particular methyl. Most preferably, groups R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, each independently, are unsubstituted C ₁ -C ₆ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl , isobutyl, tert-butyl, pentyl, hexyl and cyclohexyl, in particular methyl.

Alternatively or additionally, one or more groups of R ¹ to R ³ , R ⁴ to R ⁶ , R ⁷ to R ⁹ , R ¹⁰ to R ¹² , R ¹³ to R ¹⁵ , R ¹⁶ to R ¹⁸ , R ³¹ to R ³³ , R ³⁴ to R ³⁶ , R ³⁷ to R ^39, or R ⁴⁰ to R ⁴² (when present) together with the carbon atom to which they are attached can independently form cyclic alkyl structures such as 1-norbornyl or 1-norbornadienyl.

Alternatively or additionally, one or more of the groups R ¹ and R ² , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ¹⁰ and R ¹¹ , R ¹³ and R ¹⁴ , R ¹⁶ and R ¹⁷ , R ³¹ and R ³² , R ³⁴ and R ^35, R ³⁷ and R ³⁸ or R ⁴⁰ and R ⁴¹ (when present) together with the carbon atom to which they are bonded, independently may form cyclic alkyl structures, preferably a _{C5 7} cyclic alkyl structures such like cyclohexyl and cyclopentyl, and R ³ , R ⁶ , R ⁹ , R ¹² , R ¹⁵ , R ¹⁸ , R ³³ , R ³⁶ , R ³⁹ and R ⁴² (when present), each independently represent hydrogen, lower alkyl , trifluoromethyl or aryl, as described above, in cha tnosti unsubstituted C ₁ -C ₆ alkyl and hydrogen, especially unsubstituted C ₁ -C ₆ alkyl.

In a particularly preferred embodiment, each R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, is not hydrogen. This arrangement means that Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ are bonded to a carbon atom from X ¹ to X ¹⁰ , respectively, which do not have hydrogen atoms.

Preferably, each of R ¹ , R ⁴ , R ⁷ , R ¹⁰ , R ¹³ , R ¹⁶ , R ³¹ , R ³⁴ , R ³⁷ and R ⁴⁰ (when present) is the same substituent as defined herein application; each of R ² , R ⁵ , R ⁸ , R ¹¹ , R ¹⁴ , R ¹⁷ , R ³² , R ³⁵ , R ³⁸ and R ⁴¹ (when present) is the same substituent as defined herein; each of R ³ , R ⁶ , R ⁹ , R ¹² , R ¹⁵ , R ¹⁸ , R ³³ , R ³⁶ , R ³⁹ and R ⁴² (when present) is the same substituent as defined herein. More preferably, each of R ¹ , R ⁴ , R ⁷ , R ¹⁰ , R ¹³ , R ¹⁶ , R ³¹ , R ³⁴ , R ³⁷ and R ⁴⁰ (when present) is the same C ₁ -C ₆ alkyl, in particular unsubstituted C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl or cyclohexyl, or trifluoromethyl; each of R ² , R ⁵ , R ⁸ , R ¹¹ , R ¹⁴ , R ¹⁷ , R ³² , R ³⁵ , R ³⁸ and R ⁴¹ (when present) independently represents the same C ₁ -C ₆ alkyl, as defined above, or trifluoromethyl; and each of R ³ , R ⁶ , R ⁹ , R ¹² , R ¹⁵ , R ¹⁸ , R ³³ , R ³⁶ , R ³⁹ and R ⁴² (when present) independently represents the same C ₁ -C ₆ alkyl as defined above, or trifluoromethyl. For example: each of R ^1, R ^4, R ^7, R ^10, R ¹³ and R ¹⁶ (when present) is methyl; each of R ² , R ⁵ , R ⁸ , R ¹¹ , R ^14, and R ¹⁷ is ethyl (when present); and each of R ³ , R ⁶ , R ⁹ , R ¹² , R ¹⁵ and R ¹⁸ (when present) is n-butyl or n-pentyl.

In a particularly preferred embodiment of the present invention, each group from R ¹ to R ¹⁸ and from R ³¹ to R ⁴² (when present) represents the same substituent as defined herein. Preferably, each group from R ¹ to R ¹⁸ and from R ³¹ to R ⁴² represents the same C ₁ -C ₆ alkyl group, in particular unsubstituted C ₁ -C ₆ alkyl, such as methyl, ethyl, n-propyl , isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl or cyclohexyl, or trifluoromethyl. More preferably, each group from R ¹ to R ¹⁸ and from R ³¹ to R ⁴² represents unsubstituted C ₁ -C ₆ alkyl, in particular methyl.

As used herein, the term “adamantyl” means an adamantyl group which may be attached to Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ , respectively, at position 1 or 2. Tricyclo [3.3.1.1 {3,7}] decyl means the systematic name for the adamantyl group, suitable when Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ , respectively, can be associated in 1 or 2 position with one or two tricyclo [3.3.1.1 {3,7} ] decile groups. Preferably, Q ¹ and Q ² , as well as Q ³ , Q ⁴ and Q ⁵ , when present, are bound to the tertiary carbon of one or more adamantyl groups. In an appropriate case, when the adamantyl group is an unsubstituted adamantyl, then Q ¹ and Q ² , as well as Q ³ , Q ⁴ and Q ⁵ , when present, are preferably linked in 1 position to one or more tricyclo [3.3.1.1 { 3,7}] decyl groups, i.e. the carbon atom of the adamantyl group does not have a hydrogen atom.

The adamantyl group may, if desired, contain, together with hydrogen atoms, one or more substituents selected from lower alkyl, —OR ¹⁹ , —OC (O) R ²⁰ , halogen, nitro, —C (O) R ²¹ , —C (O) OR ^22, cyanogen, aryl, -N (R ²³⁾ R ^24, -C (O) N (R ²⁵⁾ R ^26, -C (S) (R ²⁷⁾ R ^28, -CF _3, -P (R ⁵⁶ ) R ⁵⁷ , —PO (R ⁵⁸ ) (R ⁵⁹ ), —PO ₃ H ₂ , —PO (OR ⁶⁰ ) (OR ⁶¹ ), or —SO ₃ R ⁶² , in which R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , lower alkyl, cyano and aryl are as defined herein, and groups R ⁵⁶ to R ⁶² each independently represent hydrogen lower alkyl, aryl or hetero.

Suitably, when the adamantyl group is substituted with one or more substituents as indicated above, the most preferred substituents include unsubstituted C ₁ -C ₈ alkyl, —OR ¹⁹ , —OC (O) R ²⁰ , phenyl, —C (O) OR ²² , fluoro, —SO ₃ H, —N (R ²³ ) R ²⁴ , —P (R ⁵⁶ ) R ⁵⁷ , —C (O) N (R ²⁵ ) R ^26, and —PO (R ⁵⁸ ) (R ⁵⁹ ), —CF ₃ in which R ¹⁹ is hydrogen, unsubstituted C ₁ -C ₈ alkyl or phenyl, R ²⁰ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ each independently represent hydrogen or unsubstituted C ₁ -C ₈ alkyl, from R ⁵⁶ to R ⁵⁹ , each independently is unsubstituted C ₁ -C ₈ alkyl or phenyl.

Suitably, the adamantyl group may contain, together with hydrogen atoms, up to 10 substituents as described above, preferably up to 5 substituents as described above, more preferably up to 3 substituents as described above. In a suitable case, when the adamantyl group contains, together with hydrogen atoms, one or more substituents, as defined here, all substituents are preferably identical. Preferred substituents are unsubstituted C ₁ -C ₈ alkyl and trifluoromethyl, in particular unsubstituted C ₁ -C ₈ alkyl, such as methyl. Most preferred is an adamantyl group containing only hydrogen atoms, i.e. the adamantyl group is not substituted.

Preferably, when more than one adamantyl group is present in the compound of formula I, wherein all adamantyl groups are identical.

The term "2-phosphatricyclo [3.3.1.1 {3,7}] decyl group" means a 2-phospha-adamantyl group formed by the combination of X ¹ and X ² together with Q ² to which they are attached, a 2-phospha-adamantyl group formed by the combination of X ³ and X ⁴ together with Q ¹ to which they are attached, a 2-phospha-adamantyl group formed by combining X ⁵ and X ⁶ together with Q ³ to which they are attached, a 2-phospha-adamantyl group formed by combining X ⁷ and X ⁸ together with Q ⁴ to which they are attached, and a 2-phosphaadamantyl group formed by combining X ⁹ and X ¹⁰ in the place with Q ⁵ to which they are attached, in which Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ are in position 2 of the adamantyl group with which they form one, and each of Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ represents phosphorus.

The 2-phosphatricyclo [3.3.1.1 {3,7}] decyl group (referred to herein as the 2-phospha-adamantyl group) may optionally contain, together with hydrogen atoms, one or more substituents. Suitable substituents include the same substituents as defined herein for the adamantyl group. Highly preferred substituents include lower alkyl, in particular unsubstituted C ₁ -C ₈ alkyl, in particular methyl trifluoromethyl, -OR ¹⁹ in which R ^{19 is} defined as indicated herein, in particular, is unsubstituted C ₁ -C ₈ alkyl or aryl; and 4-dodecylphenyl. When a 2-phospha-adamantyl group includes more than one substituent, it is preferred that all substituents are identical.

Preferably, when the 2-phospha-adamantyl group is substituted at one or more of positions 1, 3, 5, or 7 with a substituent, as defined herein. More preferably, the 2-phospha-adamantyl group is substituted at each of positions 1, 3, and 5. This arrangement means that the phosphorus atom of the 2-phospha-adamantyl group is bonded to carbon atoms in the adamantyl skeleton without hydrogen atoms. Most preferably, when the 2-phosphaadamantyl group is substituted at each of positions 1, 3, 5, and 7. If the 2-phosphaadamantyl group includes more than 1 substituent, then preferably all substituents are identical. Particularly preferred substituents are unsubstituted C ₁ -C ₈ alkyl and trifluoromethyl, in particular unsubstituted C ₁ -C ₈ alkyl, such as methyl.

Preferably, when the 2-phospha-adamantyl group includes additional heteroatoms other than the 2-phosphorus atom in the skeleton of the 2-phospha-adamantyl group. Suitable additional heteroatoms include oxygen and sulfur atoms, in particular oxygen atoms. More preferably, when the 2-phospha-adamantyl group includes one or more additional heteroatoms at positions 6, 9 and 10. Even more preferably, when the 2-phospha-adamantyl group includes one additional heteroatoms in each of positions 6, 9 and 10. Most preferably when the 2-phospha-adamantyl group includes two or more additional heteroatoms in the 2-phospha-adamantyl skeleton, all additional heteroatoms being identical. A particularly preferred 2-phospha-adamantyl group, which may optionally be substituted with one or more substituents, as defined herein, includes an oxygen atom at each of positions 6, 9 and 10 of the 2-phospha-adamantyl skeleton.

Highly preferred 2-phospha-adamantyl groups as defined herein include a 2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxadamantyl group, 2-phospha-1,3,5-trimethyl-6 , 9,10-trioxadamantyl group, 2-phospha-1,3,5,7-tetra (trifluoromethyl) -6,9,10-trioxadamantyl group and 2-phospha-1,3,5-tri (trifluoromethyl) -6 , 9,10-trioxadamantyl group. More preferably, when 2-phospha-adamantyl is selected from 2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxadamantyl group or 2-phospha-1,3,5-trimethyl-6,9,10- trioxadamantyl group.

Preferably, when more than one 2-phospha-adamantyl group is present in the compound of formula I, wherein all 2-phospha-adamantyl groups are identical.

As used herein, the term “congressyl” means a congressyl group (also known as a diamantyl group) that may be associated with Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ , respectively. Preferably, when Q ¹ and Q ² , Q ³ , Q ⁴ and Q ⁵ , if present, are bonded to one of the tertiary carbon atoms of the congressyl groups. Suitably, when the congressyl group is unsubstituted, Q ¹ and Q ² , as well as Q ³ , Q ⁴ and Q ⁵ , when present, are preferably associated with one or more congressional groups at position 1. The congressional group may optionally contain, together with hydrogen atoms, one or more substituents. Suitable substituents include the same substituents as indicated herein for the adamantyl group. Highly preferred substituents include unsubstituted C ₁ -C ₆ alkyl groups, in particular methyl and trifluoromethyl. Most preferably, the congressyl group is unsubstituted and contains only hydrogen atoms.

Preferably, when more than one congressyl group is present in the compound of formula I, all congressyl groups are identical.

Preferably, if one or more cyclic systems of the formula Ia, Ib, Ic, Id or Ie are present in the compound of the formula I, the groups R ⁵⁰ to R ⁵³ are each independently lower alkyl, aryl or hetero, the groups being optionally substituted and / or end as defined here. This arrangement means that Q ¹ , Q ² , Q ³ , Q ⁴ and Q ^{5 of the} cyclic system in formulas Ia to Ie, respectively, are not bonded to a carbon atom carrying a hydrogen atom. Even more preferably, when the groups R ⁵⁰ to R ⁵³ , each independently, are optionally substituted C ₁ -C ₆ alkyl, preferably unsubstituted C ₁ -C ₆ alkyl, phenyl optionally substituted with unsubstituted C ₁ -C ₆ alkyl or OR ¹⁹ where R ¹⁹ represents unsubstituted C ₁ -C ₆ alkyl or trifluoromethyl. Even more preferably, when all groups from R ⁵⁰ to R ⁵³ represent the same group as defined herein, in particular unsubstituted C ₁ -C ₆ alkyl, in particular methyl.

Preferably, when one or more cyclic systems of formulas Ia to Ie, R ⁴⁹ and R ⁵⁴ are each present in the compound of formula I, each independently is optionally substituted C ₁ -C ₆ alkyl, preferably unsubstituted C ₁ -C ₆ alkyl, phenyl, optionally substituted with unsubstituted C ₁ -C ₆ alkyl or OR ¹⁹ , where R ¹⁹ is unsubstituted C ₁ -C ₆ alkyl, trifluoromethyl or hydrogen. More preferably, when R ⁴⁹ and R ⁵⁴ represent the same group, as defined here, in particular hydrogen.

Preferably, when one or more cyclic systems of formulas Ia to Ie are present in a compound of formula I, Y ¹ to Y ⁵ are identical. Most preferably, when each from Y ¹ to Y ⁵ represents oxygen. Preferably, when more than one cyclic system of formulas Ia to Ie is present in a compound of formula I, all such cyclic systems are identical.

Preferred embodiments of the present invention include those in which:

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ) and X ⁴ represents CR ¹⁰ (R ¹¹⁾ (R ^12);

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents adamantyl, X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ) and X ⁴ represents adamantyl;

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents congressyl, X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ) and X ⁴ represents congressyl;

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), and X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of the formula Ib or 2-phosphaadamantyl group;

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents adamantyl, X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of formula Ib or a 2-phospha-adamantyl group;

X ¹ is CR ¹ (R ²⁾ (R ³⁾ X ² represents congressyl, X ³ and X ⁴ together with Q ¹ to which they are attached form a ring system of formula Ib or a 2-fosfaadamantilnuyu group;

from X ¹ to X ⁴ , each independently, are adamantyl;

from X ¹ to X ⁴ , each independently, is congressyl;

X ¹ and X ² each independently represent adamantyl, and X ³ and X ⁴ each independently represent congressyl;

X ¹ and X ³ independently represent adamantyl, and X ² and X ⁴ independently represent congressyl;

X ¹ and X ² independently represent adamantyl, X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ) and X ⁴ represents CR ¹⁰ (R ¹¹ ) (R ¹² );

X ¹ and X ² independently represent congressyl, X ³ is CR ⁷ (R ⁸⁾ (R ⁹⁾ and X ⁴ represents CR ¹⁰ (R ¹¹⁾ (R ^12);

X ¹ and X ² independently are adamantyl, and X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of the formula Ib or a 2-phospha-adamantyl group;

X ¹ and X ² independently represent congressyl, and X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of the formula Ib or a 2-phospha-adamantyl group;

X ¹ and X ² together with Q ² to which they are attached form a cyclic system of the formula Ia, and X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of the formula Ib;

X ¹ and X ² together with Q ² to which they are attached form a 2-phospha-adamantyl group, and X ³ and X ⁴ together with Q ¹ to which they are attached form a 2-phospha-adamantyl group.

Very preferred embodiments of the present invention include those in which:

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ) and X ⁴ represents CR ¹⁰ (R ¹¹⁾ (R ^12);

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents adamantyl, X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ) and X ⁴ represents adamantyl;

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents congressyl, X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ) and X ⁴ represents congressyl;

from X ¹ to X ⁴ , each independently, are adamantyl;

from X ¹ to X ⁴ , each independently, is congressyl;

X ¹ and X ² together with Q ² to which they are attached form a cyclic system of the formula Ia, and X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of the formula Ib;

X ¹ and X ² together with Q ² to which they are attached form a 2-phospha-adamantyl group, and X ³ and X ⁴ together with Q ¹ to which they are attached form a 2-phospha-adamantyl group.

Preferably when in a compound of formula ^I, X ¹ is identical to X ² and X ³ is identical to X ^4. More preferably, when X ¹ is identical to X ³ and X ⁵ , X ⁷ and X ⁹ when they are present, and X ² is identical to X ⁴ and X ⁶ , X ⁸ and X ¹⁰ when they are present. Even more preferably, when X ¹ to X ⁴ are identical. Most preferably, when X ¹ to X ⁴ are identical to each of X ⁶ to X ¹⁰ when they are present.

Preferably, when in the compound of formula I, X ¹ and X ² are identical substituents, X ³ and X ⁴ are identical substituents, X ⁵ and X ⁶ (when present) are identical substituents, X ⁷ and X ⁸ (when they are present) are identical substituents and X ⁹ and X ¹⁰ (when present) are identical substituents.

Preferably when in a compound of formula I K represents -Q ³ -A ₃ (X ⁵⁾ X ⁶ are hydrogen, lower alkyl, -CF _3, phenyl or lower alkylphenyl. More preferably, when K is —A ₃ —Q ³ (X ⁵ ) X ⁶ , hydrogen, unsubstituted C ₁ -C ₆ alkyl, unsubstituted phenyl, trifluoromethyl or C ₁ -C ₆ alkyl phenyl.

In a particularly preferred embodiment, K in the compound of formula I is hydrogen.

In an alternative embodiment, when K is not hydrogen, K is —A ₃ —Q ³ (X ⁵ ) X ⁶ . Preferably, when X ⁵ is identical to X ³ or X ¹ and X ⁶ is identical to X ² or X ⁴ . More preferably, when X ⁵ is identical and X ³ and X ¹ and X ⁶ is identical to both X ² and X ⁴ . Even more preferably, when -A ₃ -Q ³ (X ⁵ ) X ⁶ is identical to either -A ₁ -Q ² (X ¹ ) X ² or -A ₂ -Q ¹ (X ³ ) X ⁴ . Most preferably, when -A ₃ -Q ³ (X ⁵ ) X ⁶ is identical and -A ₁ -Q ² (X ¹ ) X ² and -A ₂ -Q ¹ (X ³ ) X ⁴ .

Most preferably, when K represents hydrogen in the compound of formula I.

Preferably, in the compound of formula ID is —A ₄ —Q ⁴ (X ⁷ ) X ⁸ , hydrogen, lower alkyl, CF ₃ , phenyl or lower alkyl phenyl, and E is —A ₅ —Q ⁵ (X ⁹ ) X ¹⁰ , hydrogen, lower alkyl, CF ₃ , phenyl or lower alkyl phenyl, or D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an optionally substituted phenyl ring. More preferably, when D is —A ₄ —Q ⁴ (X ⁷ ) X ⁸ , hydrogen, phenyl, C ₁ -C ₆ alkyl phenyl, unsubstituted C ₁ -C ₆ alkyl, such as methyl, ethyl, propyl, butyl, pentyl and hexyl or CF ₃ ; E represents —A ₅ —Q ⁵ (X ⁹ ) X ¹⁰ , hydrogen, phenyl, C ₁ -C ₆ alkyl phenyl, unsubstituted C ₁ -C ₆ alkyl, such as methyl, ethyl, propyl, butyl, pentyl and hexyl, or -CF ₃ ; or both D and E, together with the carbon atoms of the cyclopentadienyl ring to which they are attached, form a phenyl ring that is optionally substituted with one or more groups selected from phenyl, C ₁ -C ₆ alkylphenyl, unsubstituted C ₁ -C ₆ alkyl, or -CF ₃ .

Suitably, D and E, together with the carbon atoms of the cyclopentadienyl ring to which they are attached, form an optionally substituted phenyl ring, the metal M or its cation being attached to the indenyl ring system.

In a particularly preferred embodiment, D in the compound of formula I is hydrogen.

In an alternative embodiment, when D is not hydrogen, D is —A ₄ —Q ⁴ (X ⁷ ) X ⁸ . Preferably, when X ⁸ is identical to X ⁴ or X ² and X ⁷ is identical to X ¹ or X ³ . More preferably, when X ⁸ is identical and X ⁴ and X ² and X ⁷ is identical to X ¹ and X ³ . Even more preferably, when -A ₄ -Q ⁴ (X ⁷ ) X ⁸ is identical to either -A ₁ -Q ² (X ¹ ) X ² or -A ₂ -Q ¹ (X ³ ) X ⁴ . Most preferably, when -A ₄ -Q ⁴ (X ⁷ ) X ⁸ is identical to both -A ₂ -Q ¹ (X ³ ) X ⁴ and -A ₃ -Q ³ (X ⁵ ) X ⁶ , if present .

In a particularly preferred embodiment, E in the compound of formula I is hydrogen.

In an alternative embodiment, when E is not hydrogen, E is —A ₅ —Q ⁵ (X ⁹ ) X ¹⁰ . Preferably, when X ¹⁰ is identical to X ⁴ or X ² and X ⁹ is identical to X ¹ or X ³ . More preferably, if X ¹⁰ is identical and X ⁴ and X ² and X ⁹ is identical to X ¹ and X ³ . Even more preferably, when -A ₅ -Q ⁵ (X ⁹ ) X ¹⁰ is identical to either -A ₁ -Q ² (X ¹ ) X ² or -A ₂ -Q ¹ (X ³ ) X ⁴ . Most preferably, when -A ₅ -Q ⁵ (X ⁹ ) X ¹⁰ is identical and -A ₁ -Q ² (X ¹ ) X ² and -A ₂ -Q ¹ (X ³ ) X ⁴ and -A ₃ - Q ³ (X ⁵⁾ X ^6, and -Q ⁴ -A ₄ (X ⁷⁾ X ^8, if present.

Preferably, in a compound of formula I, if D and E, together with the carbon atoms of the cyclopentadienyl ring to which they are attached, do not form an optionally substituted phenyl ring, each of K, D, and E represents an identical substituent.

In an alternative preferred embodiment, D and E, together with the carbon atoms of the cyclopentadienyl ring to which they are attached, form an unsubstituted phenyl ring.

Very preferred embodiments of the compounds of formula I include those in which:

K, D and E are identical substituents as defined herein, in particular when K, D and E are hydrogen;

K represents hydrogen, and D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring;

K represents —A ₃ —Q ³ (X ⁵ ) X ⁶ , as defined herein, and D and E both represent H;

K represents —A ₃ —Q ³ (X ⁵ ) X ⁶ , as defined herein, and D and E, together with the carbon atoms of the cyclopentadienyl ring to which they are attached, form an unsubstituted phenyl ring;

K represents —A ₃ —Q ³ (X ⁵ ) X ⁶ , D represents —A ₄ —Q ⁴ (X ⁷ ) X ^8, and E represents —A ₅ —Q ⁵ (X ⁹ ) X ¹⁰ .

Particularly preferred compounds of formula I include those in which D and E both represent hydrogen or D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring, in particular those where and D and E both represent hydrogen.

Preferably, when in the compound of formula I, A ₁ and A ₂ , as well as A ₃ , A ₄ and A ₅ (when present), each independently, are C ₁ -C ₆ alkylene, which is optionally substituted, as defined here, for example lower alkyl groups. A ₁ and A ₂ , as well as A ₃ , A ₄ and A ₅ (when present) may suitably include a chiral carbon atom. Preferably, when lower alkylene groups, which can be represented by the symbols from A ₁ to A ₅ are not substituted. A particularly preferred lower alkylene, which may independently be A ₁ to A ₅ , is —CH ₂ - or —C ₂ H ₄ -. Most preferably, if each of A ₁ and A ₂ , as well as A ₃ , A ₄ and A ₅ (when present) is the same lower alkylene, as defined here, in particular —CH ₂ -.

In the compound of formula I, preferably each Q ¹ and Q ² and Q ^3, Q ⁴ and Q ⁵ (when present) are the same. Most preferably, if each of Q ¹ and Q ² , as well as Q ³ , Q ⁴ and Q ⁵ (when present) is phosphorus.

Specialists in this field should take into account that the compounds of formula I (indicated as (b) above) can act as ligands that form a coordination bond with a Group VIIIB metal or its compound (indicated as (a) above) to form compounds of the invention . Typically, a Group VIIIB metal or its compound (a) forms a coordination bond with one or more phosphorus, arsenic and / or antimony atoms of a compound of Formula I. It should be noted that compounds of Formula I may be referred to, in the broad sense, as “metallocenes” "

Suitably, when n = 1 and L ₁ represents an optionally substituted cyclopentadienyl or indenyl group, the compounds of formula I may contain either two cyclopentadienyl rings, or two indenyl rings, or one indenyl and one cyclopentadienyl ring (each of these ring systems may be optionally substituted as described here). Such compounds can be referred to as “sandwich compounds”, since metal M or its cation is placed in the middle between the planes of two ring systems. The corresponding cyclopentadienyl and / or indenyl cyclic systems can be substantially coplanar to each other or they can be tilted with respect to each other (usually referred to as tilted metallocenes). Alternatively, when n = 1 and L ₁ is aryl, the compounds of the invention may contain either one cyclopentadienyl or one indenyl ring (each of the ring systems may optionally be substituted as described herein) or one aryl ring which is optionally substituted, as defined here. In a suitable case, when n = 1 and L ₁ represents aryl, then the metal M of the compounds of formula I, as defined here, is usually in the form of a metal cation.

In a particularly preferred embodiment of the invention, in the compound of formula I, n = 1, L ₁ is, as defined herein, and m = 0.

Preferably, when in the compound of formula I n = 1, L ₁ is cyclopentadienyl, indenyl or aryl, each of these rings optionally substituted with one or more substituents selected from hydrogen, lower alkyl, halogen, cyan, nitro, -OR ¹⁹ , -OC (O) R ^20, -C (O) R ^21, -C (O) OR ^22, -N (R ²³⁾ R ^24, -C (O) N (R ²⁵⁾ R ^26, -C (S ) (R ²⁷ ) R ²⁸ , -SR ²⁹ , -C (O) SR ³⁰ , CF ₃ or ferrocenyl (this term means that the cyclopentadienyl, indenyl or aryl ring, which may be L ₁ , is directly linked to cyclopentadienyl ferroc ring nilnoy group) in which the groups of R ¹⁹ to R ³⁰ are defined as herein. More preferably, if the cyclopentadienyl, indenyl or aryl ring, which may be L ₁ , is substituted, it is preferably substituted with one or more substituents selected from unsubstituted C ₁ -C ₆ alkyl, halogen, cyan, -OR ¹⁹ , - OC (O) R ²⁰ , -C (O) R ²¹ , -C (O) OR ²² , -N (R ²³ ) R ²⁴ , where R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent hydrogen or C ₁ -C ₆ alkyl. Even more preferably, if the cyclopentadienyl, indenyl or aryl ring which L ₁ may represent is substituted, it is preferably substituted with one or more substituents selected from unsubstituted C ₁ -C ₆ alkyl.

Preferably, when n = 1, L ₁ is cyclopentadienyl, indenyl, phenyl or naphthyl, optionally substituted as defined herein. Preferably, the cyclopentadienyl, indenyl, phenyl or naphthyl groups are unsubstituted. More preferably, when L ₁ is cyclopentadienyl, indenyl or phenyl, each of these rings being unsubstituted. Most preferably, L ₁ is unsubstituted cyclopentadienyl.

Alternatively, when n = 0, the compounds of the invention contain only one cyclopentadienyl or indenyl ring (each of these ring systems may optionally be substituted as defined here). Such compounds may be referred to as “semi-sandwich compounds”. Preferably, when n = 0, then m has a value from 1 to 5, so that the metal M in the compound of formula I has an electronic number of 18. In other words, when the metal M in the compound of formula I is iron, the total number of electrons provided by the ligands L ₂ is usually equal to five.

In a particularly preferred alternative embodiment, in the compound of Formula I n = 0, L ₂ is defined as herein defined, and m = 3 or 4, particularly 3.

Preferably, when n is zero and m is not zero in the compound of formula I, L ₂ represents one or more ligands, each of which is independently selected from lower alkyl, halogen, —CO, —P (R ⁴³ ) (R ⁴⁴ ) R ⁴⁵ or -N (R ⁴⁶ ) (R ⁴⁷ ) R ⁴⁸ . More preferably, when L ₂ is one or more ligands, each of which is independently selected from unsubstituted C ₁ -C ₄ alkyl, halogen, in particular chlorine, —CO, —P (R ⁴³ ) (R ⁴⁴ ) R ⁴⁵ or - N (R ⁴⁶ ) (R ⁴⁷ ) R ⁴⁸ , wherein R ⁴³ to R ^{48 is} independently selected from hydrogen, unsubstituted C ₁ -C ₆ alkyl or aryl, such as phenyl.

In a suitable case, the metal M or a cation of this metal in the compound of formula I is usually linked to the cyclopentadienyl ring (s), the cyclopentadienyl part of the indenyl ring (s), if present, the aryl ring, if present, and / or L ₂ ligands, if any are present. Typically, when the cyclopentadienyl ring or the cyclopentadienyl part of the indenyl ring exhibits a pentagapto type bond with the metal; however, other types of bonds between the cyclopentadienyl ring or cyclopentadienyl part of the indenyl ring and the metal, such as trigaptocoordination, are also included in the scope of this invention.

Most preferably, if in the compound of formula I n = 1, m = 0 and L _{1 is} defined, as indicated here, in particular, unsubstituted cyclopentadienyl.

The term “M is a metal of group VIB or VIIIB” in the compound of formula I includes metals such as Cr, Mo, W, Fe, Co, Ni, Ru and Rh. For the avoidance of doubt, references to metals of groups VIB or VIIIB here include metals of groups 6, 8, 9 and 10 in the modern Periodic system of elements.

By the term “cation of a given metal”, the applicant means that the metal (M) of group VIB or VIIIB in the compound of formula I, as defined herein, has a positive charge. Suitably, the metal cation may be in salt form or may contain weakly coordinated anions derived from hydrohalic, nitric acid; sulfuric acid; lower alkanoic (up to C ₁₂ ) acids such as acetic acid and propionic acid; sulfonic acids such as methanesulfonic acid, chlorosulfonic acid, fluorosulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, toluenesulfonic acid, for example p-toluenesulfonic acid, tert-butyl sulfonic acid and 2-hydroxypropanesulfonic acid; sulfonated ion exchange resins; perhalogenic acid such as perchloric acid; perfluorinated carboxylic acid such as trichloroacetic acid and trifluoroacetic acid; phosphoric acid; phosphonic acid such as benzene phosphonic acid; and acids obtained by the reaction of Lewis acids and Bronsted acids. Other sources that may give suitable anions include tetraphenylborate derivatives.

Preferably, M is a metal of group VIB or VIIIB. In other words, the total electron number for metal M is 18.

Preferably, in the compound of formula I, M represents Cr, Mo, Fe, Co or Ru, or a cation of this metal. Even more preferably, M represents Cr, Fe, Co or Ru or a cation of this metal. Most preferably, when M is selected among Group VIIIB metals or their cations. A particularly preferred Group VIIIB metal is Fe. Although the metal M, as defined here, may be in the form of a cation, it is preferable when it practically does not carry a residual charge due to coordination with L ₁ and / or L ₂ , as defined here.

As used herein, the term “aryl” includes six to ten-membered carbocyclic aromatic groups such as phenyl and naphthyl, these groups optionally substituted with one or more substituents selected from aryl, lower alkyl (wherein the alkyl group may itself be optionally substituted or terminated as defined below), hetero, halo, cyano, nitro, -OR ^19, -OC (O) R ^20, -C (O) R ^21, -C (O) OR ^22, -N (R ²³⁾ R ²⁴ , —C (O) N (R ²⁵ ) R ²⁶ , —SR ²⁹ , —C (O) SR ^30, or —C (S) N (R ²⁷ ) R ²⁸ , in which groups R ¹⁹ to R ³⁰ , each independently represent hydrogen, aryl or lower alkyl (wherein the alkyl group may itself be optionally substituted or terminated as indicated below). Preferred aryl groups which may be represented by K, D, E, R ¹ to R ⁵⁵ and L ₁ and which may be substituted by adamantyl, 2-phospha-adamantyl, congressyl or lower alkyl include phenyl, which is optionally substituted with one or by several substituents selected from C ₁ -C ₆ alkyl (wherein the alkyl group may itself optionally be substituted or terminated as defined below), OR ¹⁹ , R ¹⁹ , halogen and NR ²³ (R ²⁴ ), where R ¹⁹ , R ²³ and R ²⁴ independently represent hydrogen or lower alkyl. Further preferred aryl groups include phenyl, which is optionally substituted with one or more substituents selected from unsubstituted C ₁ -C ₆ alkyl, OR ¹⁹ in which R ¹⁹ is hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular unsubstituted C ₁ -C ₆ alkyl.

As used herein, the term “hetero” includes ring systems from four to twelve membered, preferably four to ten membered, rings of which contain one or more heteroatoms selected from nitrogen, oxygen, sulfur, and combinations thereof, and rings of which contain one or more double bonds or are non-aromatic, partially aromatic or fully aromatic in nature. Ring systems may be monocyclic, bicyclic or fused. Each “hetero” group identified here is optionally substituted with one or more substituents selected from halogen, cyano, nitro, oxo, lower alkyl (wherein the alkyl group itself may optionally be substituted or terminated as indicated below), -OR ¹⁹ , - OC (O) R ²⁰ , -C (O) R ²¹ , -C (O) OR ²² , -N (R ²³ ) R ²⁴ , -C (O) N (R ²⁵ ) R ²⁶ , -SR ²⁹ , - C (O) SR ³⁰ or —C (S) N (R ²⁷ ) R ²⁸ , wherein R ¹⁹ to R ³⁰ each independently represents hydrogen, aryl or lower alkyl (wherein the alkyl group itself may optionally be substituted or terminated as defined below). The term “hetero” thus includes groups such as optionally substituted azetidinyl, pyrrolidinyl, imidazolyl, indolyl, furanyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, thiadiazolyl, triazolyl, oxatriazolyl, triatriazolyl, pyridinyl pyridinyl , quinolinyl, isoquinolinyl, piperidinyl, pyrazolyl and piperazinyl. The substitution in the heterocycle may be at the carbon atom of the heterocycle or, where appropriate, at one or more heteroatoms.

“Hetero” groups may also be in the form of an N-oxide.

The term “lower alkyl” as used herein means C ₁ -C ₁₀ alkyl and includes methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl groups. Unless otherwise indicated, alkyl groups may, when there are a sufficient number of carbon atoms, be linear or branched, be saturated or unsaturated, be cyclic, acyclic or partially cyclic / acyclic, and / or be substituted or terminated by one or more substituents selected from halogen, cyano, nitro, -OR ¹⁹ , -OC (O) R ²⁰ , -C (O) R ²¹ , -C (O) OR ²² , -N (R ²³ ) R ²⁴ , -C (O) N ( R ²⁵⁾ R ^26, -SR ^29, -C (O) SR ^30, -C (S) N (R ²⁷⁾ R ^28, or hetero aryl in which of R ¹⁹ to R ³⁰ each independently represent hydrogen , aryl or lower alkyl, and / or interrupt tsya one or more oxygen or sulfur atoms or a silane or dialkilkremnievymi groups.

Lower alkyl groups, which may be represented by groups denoted by R ¹ to R ⁶² , K, D, E, and L ₂ and which may be substituted by aryl, hetero and L ₁ , may, when there are a sufficient number of carbon atoms, be linear or branched, saturated or unsaturated, cyclic, acyclic or partially cyclic / acyclic, and / or interrupted by one or more oxygen or sulfur atoms or silane or dialkyl silicon groups, and / or substituted by one or more substituents selected from halogen, cyano, nitro, -OR ¹⁹ , -OC (O) R ²⁰ , -C (O) R ²¹ , -C (O) OR ²² , -N (R ²³ ) R ²⁴ , -C (O) N ( R ²⁵ ) R ²⁶ , -SR ²⁹ , -C (O) SR ³⁰ , -C (S) N (R ²⁷ ) R ²⁸ , aryl or hetero, in which the groups from R ¹⁹ to R ³⁰ each independently represent hydrogen, aryl or lower alkyl.

Similarly, the term “lower alkylene” as used herein, which is A ₁ and A ₂ , as well as A ₃ , A ₄ and A ₅ (when present) in the compound of formula I, when used here, includes C ₁ - With ₁₀ , which can be connected at two positions of the group and in all other respects are defined in the same way as "lower alkyl".

Halogen-containing groups that may be represented by L ₂ and with which the above groups may be substituted or terminated include fluorine, chlorine, bromine or iodine.

When a compound of formula I contains an alkenyl group, cis- (E) and trans- (Z) isomerism may also occur. The present invention includes individual stereoisomers of a compound of formula I and, where optional, their individual tautomeric forms, together with their mixtures. Separation of diastereomers or cis and trans isomers can be achieved using conventional techniques, for example, by fractional crystallization, chromatography or HPLC of a stereoisomeric mixture of a compound of formula I or the corresponding salt or derivative thereof. The individual enantiomer of a compound of formula I can also be obtained from the corresponding optically pure intermediate either by resolution, such as HPLC, of the corresponding racemate using a suitable chiral carrier, or by fractional crystallization of diastereomeric salts obtained by reacting the corresponding racemate with the corresponding optically active acid or base, therefore that is suitable.

All stereoisomers are included in the scope of the invention.

Suitable Group VIIIB metals or compounds thereof, which may be combined with a compound of Formula I to form compounds of the invention, include cobalt, nickel, palladium, rhodium and platinum. Preferably, the Group VIIIB metal is palladium or a compound thereof. Suitable compounds of such Group VIIIB metals include salts of such metals with the acids indicated below or compounds containing weakly coordinated anions derived from the following acids: nitric acid; sulfuric acid; lower alkanoic (up to C ₁₂ ) acids, such as acetic acid or propionic acid; sulfonic acids such as methanesulfonic acid, chlorosulfonic acid, fluorosulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, toluenesulfonic acid, for example p-toluenesulfonic acid, tert-butyl sulfonic acid and 2-hydroxypropanesulfonic acid; sulfonated ion exchange resins; perhalogen acid, such as perchloric acid; perfluorinated carboxylic acid such as trichloroacetic acid and trifluoroacetic acid; phosphoric acid; phosphonic acid such as benzene phosphonic acid; and acids obtained by the reaction of Lewis acids and Bronsted acids. Other sources that may give suitable anions include tetraphenylborate derivatives. Additionally, nullovalent palladium with labile ligands can be used, for example, tri (dibenzylideneacetone) dipalladium. Zero-valent Group VIIIB metals with labile ligands are preferably used.

Suitably, the compounds of the invention, when used to catalyze the carbonylation of ethylenically unsaturated compounds, include an anion source. In a convenient case, this source of anions can be obtained by combining a metal compound of group VIIIB, as described in the previous paragraph, with a compound of formula I. Alternatively or additionally, a separate source of anions can be added to the compounds of this invention, as noted above. Preferably, if the source of anions is obtained from an acid having a pKa of less than 4, more preferably a pKa of less than 3, measured at 18 ° C. in an aqueous solution.

Particularly preferred compounds of formula I include those in which:

(one)

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ), X ⁴ represents CR ¹⁰ (R ¹¹⁾ (R ¹²⁾ wherein each group of R ¹ to R ¹² independently represents unsubstituted _C1-C6 alkyl or trifluoromethyl, particularly where each of R ¹ to R ¹² are identical, in particular, when each group R ¹ to R ¹² is unsubstituted C ₁ -C ₆ alkyl, in particular methyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

K, D and E are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

Q ¹ and Q ² both represent phosphorus;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, in particular unsubstituted cyclopentadienyl, and m = 0.

(2)

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ), X ⁴ represents CR ¹⁰ (R ¹¹ ) (R ¹² ); K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ represents CR ¹³ (R ¹⁴ ) (R ¹⁵ ) and X ⁶ represents CR ¹⁶ (R ¹⁷ ) (R ¹⁸ );

each group from R ¹ to R ¹⁸ independently represents unsubstituted C ₁ -C ₆ alkyl or trifluoromethyl, in particular when the groups from R ¹ to R ¹⁸ are identical, in particular when each group from R ¹ to R ¹⁸ is unsubstituted C ₁ -C ₆ alkyl, in particular methyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² and Q ³ represents phosphorus;

D and E are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, in particular unsubstituted cyclopentadienyl, and m = 0.

(3)

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ), X ⁴ represents CR ¹⁰ (R ¹¹ ) (R ¹² ); K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ represents CR ¹³ (R ¹⁴ ) (R ¹⁵ ) and X ⁶ represents CR ¹⁶ (R ¹⁷ ) (R ¹⁸ );

each group from R ¹ to R ¹⁸ independently represents unsubstituted C ₁ -C ₆ alkyl or trifluoromethyl, in particular when the groups from R ¹ to R ¹⁸ are identical, in particular when each group from R ¹ to R ¹⁸ is unsubstituted C ₁ -C ₆ alkyl, in particular methyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² and Q ³ represents phosphorus;

D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, in particular unsubstituted cyclopentadienyl, and m = 0.

(four)

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ), X ⁴ represents CR ¹⁰ (R ¹¹ ) (R ¹² ), in which each group R ¹ to R ¹² independently is unsubstituted C ₁ -C ₆ alkyl or trifluoromethyl, in particular when the groups R ¹ to R ¹² are identical, in particular when each group R ¹ to R ¹² is unsubstituted C ₁ -C ₆ alkyl, in particular methyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

Q ¹ and Q ² both represent phosphorus;

K represents hydrogen or C ₁ -C ₆ alkyl, in particular hydrogen;

D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, in particular unsubstituted cyclopentadienyl, and m = 0.

(5)

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ), X ⁴ represents CR ¹⁰ (R ¹¹ ) (R ¹² );

E is —CH ₂ —Q ⁵ (X ⁹ ) X ¹⁰ , wherein X ⁹ is CR ³⁷ (R ³⁸ ) (R ³⁹ ) and X ¹⁰ is CR ⁴⁰ (R ⁴¹ ) (R ⁴² );

each group R ¹ to R ¹² and R ³⁷ to R ⁴² independently represents unsubstituted C ₁ -C ₆ alkyl or trifluoromethyl, in particular when the groups R ¹ to R ¹² and R ³⁷ to R ⁴² are identical, in particular when each group from R ¹ to R ¹² and from R ³⁷ to R ⁴² is unsubstituted C ₁ -C ₆ alkyl, in particular methyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² and Q ⁵ represents phosphorus;

D and K are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(6)

X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ), X ⁴ represents CR ¹⁰ (R ¹¹ ) (R ¹² );

K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ represents CR ¹³ (R ¹⁴ ) (R ¹⁵ ) and X ⁶ represents CR ¹⁶ (R ¹⁷ ) (R ¹⁸ );

D is —CH ₂ —Q ⁴ (X ⁷ ) X ⁸ , wherein X ⁷ is CR ³¹ (R ³² ) (R ³³ ) and X ⁸ is CR ³⁴ (R ³⁵ ) (R ³⁶ );

E is —CH ₂ —Q ⁵ (X ⁹ ) X ¹⁰ , wherein X ⁹ is CR ³⁷ (R ³⁸ ) (R ³⁹ ) and X ¹⁰ is CR ⁴⁰ (R ⁴¹ ) (R ⁴² );

each group from R ¹ to R ¹⁸ and from R ³¹ to R ⁴² independently represents unsubstituted C ₁ -C ₆ alkyl or trifluoromethyl, in particular when the groups from R ¹ to R ¹⁸ and from R ³¹ to R ⁴² are identical, in particular when each group R ¹ to R ¹⁸ and R ³¹ to R ⁴² is unsubstituted C ₁ -C ₆ alkyl, in particular methyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ represents phosphorus;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(7)

X ¹ , X ² , X ³ and X ⁴ independently represent adamantyl, in particular when X ¹ to X ⁴ represent the same adamantyl group;

A ₁ and A _{2 are the} same and are —CH ₂ -;

K, D and E are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

Q ¹ and Q ² both represent phosphorus;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(8)

X ¹ , X ² , X ³ and X ⁴ independently represent adamantyl, in particular when X ¹ to X ⁴ represent the same adamantyl group;

K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ and X ⁶ independently represent adamantyl, in particular when X ¹ to X ⁶ represent the same adamantyl group;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² and Q ³ represents phosphorus;

D and E are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(9)

X ¹ , X ² , X ³ and X ⁴ independently represent adamantyl, in particular when X ¹ to X ⁴ represent the same adamantyl group;

K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ and X ⁶ independently represent adamantyl, in particular when X ¹ to X ⁶ represent the same adamantyl group;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² and Q ³ represents phosphorus;

D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(10)

X ¹ , X ² , X ³ and X ⁴ independently represent adamantyl, in particular when X ¹ to X ⁴ represent the same adamantyl group;

A ₁ and A _{2 are the} same and are —CH ₂ -;

Q ¹ and Q ² both represent phosphorus;

K represents hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(eleven)

X ¹ , X ² , X ³ and X ⁴ independently represent adamantyl;

K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ and X ⁶ independently are adamantyl;

D represents —CH ₂ —Q ⁴ (X ⁷ ) X ⁸ in which X ⁷ and X ⁸ independently are adamantyl;

E represents —CH ₂ —Q ⁵ (X ⁹ ) X ¹⁰ , wherein X ⁹ and X ¹⁰ independently represent adamantyl, in particular when X ¹ to X ¹⁰ represent the same adamantyl group;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ represents phosphorus;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(12)

X ¹ and X ² together with Q ² to which they are attached represent 2-phosphaadamantyl;

X ³ and X ⁴ together with Q ¹ to which they are attached represent 2-phosphaadamantyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

K, D and E are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

Q ¹ and Q ² both represent phosphorus;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(13)

X ¹ and X ² together with Q ² to which they are attached represent 2-phosphaadamantyl;

X ³ and X ⁴ together with Q ¹ to which they are attached represent 2-phosphaadamantyl;

K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ and X ⁶ together with Q ³ to which they are attached represent 2-phospha-adamantyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² and Q ³ represents phosphorus;

D and E are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(fourteen)

X ¹ and X ² together with Q ² to which they are attached represent 2-phosphaadamantyl;

X ³ and X ⁴ together with Q ¹ to which they are attached represent 2-phosphaadamantyl;

K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ and X ⁶ together with Q ³ to which they are attached represent 2-phospha-adamantyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² and Q ³ represents phosphorus;

D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(fifteen)

X ¹ and X ² together with Q ² to which they are attached represent 2-phosphaadamantyl;

X ³ and X ⁴ together with Q ¹ to which they are attached represent 2-phosphaadamantyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

Q ¹ and Q ² both represent phosphorus;

K represents hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(16)

X ¹ and X ² together with Q ² to which they are attached represent 2-phosphaadamantyl;

X ³ and X ⁴ together with Q ¹ to which they are attached represent 2-phosphaadamantyl;

K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ and X ⁶ together with Q ³ to which they are attached represent 2-phospha-adamantyl;

D represents —CH ₂ —Q ⁴ (X ⁷ ) X ⁸ in which X ⁷ and X ⁸ together with Q ⁴ to which they are attached are 2-phospha-adamantyl;

E is —CH ₂ —Q ⁵ (X ⁹ ) X ¹⁰ , wherein X ⁹ and X ^10, together with Q ⁵ to which they are attached, are 2-phospha-adamantyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ represents phosphorus;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(17)

X ¹ and X ² together with Q ² to which they are attached form a cyclic system of the formula Ia, X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of the formula Ib in which Y ¹ and Y ² , both are oxygen, R ⁵⁰ to R ^{53 are} independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ are hydrogen;

A ₁ and A _{2 are the} same and are —CH ₂ -;

K, D and E are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

Q ¹ and Q ² both represent phosphorus;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(eighteen)

X ¹ and X ² together with Q ² to which they are attached form a cyclic system of the formula Ia, X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of the formula Ib in which Y ¹ and Y ² , both are oxygen, R ⁵⁰ to R ^{53 are} independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ are hydrogen;

K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ in which X ⁵ and X ⁶ together with Q ³ to which they are attached form a cyclic system of formula Ic in which Y ³ is oxygen, from R ⁵⁰ up to R ^{53 are} independently selected from hydrogen, unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ are hydrogen;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² and Q ³ represents phosphorus;

D and E are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(19)

X ¹ and X ² together with Q ² to which they are attached form a cyclic system of the formula Ia, X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of the formula Ib in which Y ¹ and Y ² , both are oxygen, R ⁵⁰ to R ^{53 are} independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ are hydrogen;

K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ in which X ⁵ and X ⁶ together with Q ³ to which they are attached form a cyclic system of formula Ic in which Y ³ is oxygen, from R ⁵⁰ up to R ^{53 are} independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ are hydrogen;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² and Q ³ represents phosphorus;

D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(twenty)

X ¹ and X ² together with Q ² to which they are attached form a cyclic system of the formula Ia, X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of the formula Ib in which Y ¹ and Y ² , both are oxygen, R ⁵⁰ to R ^{53 are} independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ are hydrogen;

A ₁ and A _{2 are the} same and are —CH ₂ -;

Q ¹ and Q ² both represent phosphorus;

K represents hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(21)

X ¹ and X ² together with Q ² to which they are attached form a cyclic system of the formula Ia, X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of the formula Ib in which Y ¹ and Y ² , both are oxygen, R ⁵⁰ to R ^{53 are} independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ are hydrogen;

K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ in which X ⁵ and X ^6, together with Q ³ to which they are attached, form a ring system with the formula Ic in which Y ³ represents oxygen, from R ⁵⁰ to R ^{53 are} independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ are hydrogen;

D is —CH ₂ —Q ⁴ (X ⁷ ) X ⁸ in which X ⁷ and X ^8, together with Q ⁴ to which they are attached, form a cyclic system of formula Ic in which Y ³ is oxygen, from R ⁵⁰ up to R ^{53 are} independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ are hydrogen;

E is —CH ₂ —Q ⁵ (X ⁹ ) X ¹⁰ , wherein X ⁹ and X ^10, together with Q ⁵ to which they are attached, form a cyclic system of formula Ie in which Y ⁵ is oxygen, and from R ⁵⁰ to R ^{53 are} independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ are hydrogen;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ represents phosphorus;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(22)

X ¹ , X ² , X ³ and X ⁴ independently represent congressyl, in particular when X ¹ to X ⁴ represent the same congressyl group;

A ₁ and A _{2 are the} same and are —CH ₂ -;

K, D and E are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

Q ¹ and Q ² both represent phosphorus;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(23)

X ¹ , X ² , X ³ and X ⁴ independently represent congressyl, in particular when X ¹ to X ⁴ represent the same congressyl group;

K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ and X ⁶ independently represent congressyl, in particular when X ¹ to X ⁶ represent the same congressional group;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² and Q ³ represents phosphorus;

D and E are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(24)

X ¹ , X ² , X ³ and X ⁴ independently represent congressyl, in particular when X ¹ to X ⁴ represents the same congressyl group;

K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ and X ⁶ independently represent congressyl, in particular when X ¹ to X ⁶ represent the same congressional group;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² and Q ³ represents phosphorus;

D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(25)

X ¹ , X ² , X ³ and X ⁴ independently represent congressyl, in particular when X ¹ to X ⁴ represents the same congressyl group;

A ₁ and A _{2 are the} same and are —CH ₂ -;

Q ¹ and Q ² both represent phosphorus;

K represents hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(26)

X ¹ , X ² , X ³ and X ⁴ independently represent congressyl;

K represents —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ and X ⁶ independently represent congressyl;

D represents —CH ₂ —Q ⁴ (X ⁷ ) X ⁸ wherein X ⁷ and X ⁸ independently represent congressyl;

E represents —CH ₂ —Q ⁵ (X ⁹ ) X ¹⁰ , wherein X ⁹ and X ¹⁰ independently represent congressyl, in particular when X ¹ to X ¹⁰ represent the same congressional group;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ represents phosphorus;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(27)

X ¹ and X ³ independently represent adamantyl, in particular when X ¹ and X ³ represent the same adamantyl group;

X ² represents CR ⁴ (R ⁵ ) (R ⁶ ) and X ⁴ represents CR ¹⁰ (R ¹¹ ) (R ¹² ), in which each of R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ and R ¹² independently represents C ₁ -C ₆ alkyl or trifluoromethyl, in particular when the groups R ⁴ to R ⁶ and R ¹⁰ to R ¹² are identical, preferably when each group is R ⁴ to R ⁶ and R ¹⁰ to R ¹² represents unsubstituted C ₁ -C ₆ alkyl, in particular methyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

K, D and E are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

Q ¹ and Q ² both represent phosphorus;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(28)

X ¹ and X ³ independently represent adamantyl, in particular when X ¹ and X ³ represent the same adamantyl group;

K is —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ is adamantyl, in particular when X ¹ , X ³ and X ⁵ are the same adamantyl group;

X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), X ⁴ represents CR ¹⁰ (R ¹¹ ) (R ¹² ), X ⁶ represents CR ¹⁶ (R ¹⁷ ) (R ¹⁸ ), in which each group is from R ⁴ to R ⁶ , R ¹⁰ to R ^12, and R ¹⁶ to R ¹⁸ independently are C ₁ -C ₆ alkyl or trifluoromethyl, in particular when groups are R ⁴ to R ⁶ , R ¹⁰ to R ^12, and R ¹⁶ to R ¹⁸ are identical, in particular when each group is R ⁴ to R ⁶ , R ¹⁰ to R ¹² and R ¹⁶ to R ¹⁸ is unsubstituted C ₁ -C ₆ alkyl, in particular methyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² and Q ³ represents phosphorus;

D and E are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(29)

X ¹ and X ³ independently represent adamantyl, in particular when X ¹ and X ³ represent the same adamantyl group;

K is —CH ₂ —Q ³ (X ⁵ ) X ⁶ wherein X ⁵ is adamantyl, in particular when X ¹ , X ³ and X ⁵ are the same adamantyl group;

X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), X ⁴ represents CR ¹⁰ (R ¹¹ ) (R ¹² ), X ⁶ represents CR ¹⁶ (R ¹⁷ ) (R ¹⁸ ), in which each group is from R ⁴ to R ⁶ , R ¹⁰ to R ^12, and R ¹⁶ to R ¹⁸ independently are C ₁ -C ₆ alkyl or trifluoromethyl, in particular when groups are R ⁴ to R ⁶ , R ¹⁰ to R ^12, and R ¹⁶ to R ¹⁸ are identical, in particular when each group is R ⁴ to R ⁶ , R ¹⁰ to R ¹² and R ¹⁶ to R ¹⁸ is unsubstituted C ₁ -C ₆ alkyl, in particular methyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

each of Q ¹ , Q ² and Q ³ represents phosphorus;

D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

(thirty)

X ¹ and X ³ independently represent adamantyl, in particular when X ¹ and X ³ represent the same adamantyl group;

X ² represents CR ⁴ (R ⁵ ) (R ⁶ ) and X ⁴ represents CR ¹⁰ (R ¹¹ ) (R ¹² ), in which each of R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ and R ¹² independently represents C ₁ -C ₆ alkyl or trifluoromethyl, in particular when the groups R ⁴ to R ⁶ and R ¹⁰ to R ¹² are identical, in particular when each group is R ⁴ to R ⁶ and R ¹⁰ to R ¹² represents unsubstituted C ₁ -C ₆ alkyl, in particular methyl;

A ₁ and A _{2 are the} same and are —CH ₂ -;

Q ¹ and Q ² both represent phosphorus;

K represents hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen;

D and E together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an unsubstituted phenyl ring;

M represents Fe;

n = 1 and L ₁ represents cyclopentadienyl, particularly unsubstituted cyclopentadienyl, and m = 0.

According to a second aspect, the present invention provides a method for preparing compounds of the invention comprising a combination of (a) a Group VIIIB metal or a compound thereof, as defined herein; with (b) a compound of formula I, as defined herein.

In a convenient case, the compounds of the invention can be prepared by dissolving a Group VIIIB metal or a compound thereof, as defined herein, in a suitable solvent, such as the main end product of a carbonylation reaction, for example methylpropanoate, when the carbonylated ethylenically unsaturated compound is ethylene in the presence of methanol, or methylnonanoate, when it is intended for carbonylation of octene in the presence of methanol. Preferably, the reactants are mixed at room temperature in an inert atmosphere (e.g., nitrogen). The molar ratio of the compound of formula I (indicated by (b)) to the metal of group VIIIB or its compound (indicated by (a)) is preferably in the range from 1: 1 to 5: 1, more preferably in the range from 1: 1 to 3: 1, most preferably in the range from 1: 1 to 1: 1.25. The possibility of using such low molar ratios is an advantage, since it prevents the use of excess compounds of the formula I and, therefore, minimizes the consumption of these usually expensive compounds. The compounds of the invention are suitably prepared in a separate step prior to their in situ use in the carbonylation reaction of an ethylenically unsaturated compound. As noted above, the compounds of the invention may include additional anions obtained from the corresponding Group VIIIB compound, if applicable, and / or by adding a separate source of anions. If a separate source of anions is used, they can be added to the compounds of the invention before use in the carbonylation reaction. Alternatively or additionally, a separate source of anions may be added to the carbonylation reaction.

According to a third aspect, the present invention provides a compound of formula I as defined herein.

According to a fourth aspect, the present invention provides a process for preparing a compound of formula I, which comprises reacting a compound of formula II in which A ₁ , A ₂ , K, D, E, M, L ₁ , L ₂ , n and m are as specified for the compound formulas I, and LG ₁ and LG ₂ are suitable leaving groups,

with a compound of formula IIIa and IIIb,

in which X ¹ represents CR ¹ (R ² ) (R ³ ), congressyl or adamantyl, X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), congressil or adamantyl, or X ¹ and X ² together with Q ² to which they are attached form a 2-phosphaadamantyl group, or X ¹ and X ² together with Q ² to which they are attached form a cyclic system of formula Ia;

in which X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ), congressyl or adamantyl, X ⁴ represents CR ¹⁰ (R ¹¹ ) (R ¹² ), congressil or adamantyl, or X ³ and X ⁴ together with Q ¹ to which they are attached form a 2-phosphaadamantyl group, or X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of formula Ib;

all groups from R ¹ to R ¹² , adamantyl, congressyl, Q ¹ and Q ² , 2-phospha-adamantyl and cyclic systems of formulas Ia and Ib are defined as indicated for the compound of formula I.

Suitable leaving groups, which may be independently designated LG ₁ and LG ₂ , include groups that are easily displaced by nucleophilic attack with phosphine, arsine or stilbene derivatives IIIa and IIIb. Examples of such groups include halogen, in particular bromine or iodine, —NR ²³ R ²⁴ , where R ²³ and R ²⁴ , both are lower alkyl, in particular methyl, and hydroxyl in protonated form or not. Preferably, LG ₁ and LG ₂ are each independently —NMe ₂ or hydroxyl. Most preferably, when both LG ₁ and LG ₂ are —NMe ₂ or, LG ₁ and LG ₂ are —NMe ₂ or hydroxyl, respectively.

The reaction can be carried out using methods that are well known to specialists in this field. For example, the reaction can be carried out by heating a solution of a compound of formula II with a compound of formula IIIa and IIIb in anhydrous acetic acid at a temperature of from 70 to 90 ° C, preferably about 80 ° C, in an inert atmosphere such as a nitrogen atmosphere.

Preferably, when the compound of formula IIIa is HQ ² (CR ¹ (R ² ) (R ³ )) CR ⁴ (R ⁵ ) (R ⁶ ), then the compound of formula IIIb is HQ ¹ (CR ⁷ (R ⁸ ) (R ⁹ )) CR ¹⁰ (R ¹¹ ) (R ¹² ) in which Q ^{1 is} the same as Q ² and R ^{1 is} the same as R ⁷ , R ^{2 is} the same as R ⁸ , R ^{3 is} the same as R ⁹ , R ^{4 is} the same as R ¹⁰ , R ^{5 is} the same as R ¹¹ , and R ^{6 is} the same as R ¹² .

Preferably, when the compound of formula IIIa is HQ ² (X ¹ ) X ² in which X ¹ and X ^{2 are} independently adamantyl, then the compound of formula IIIb is HQ ¹ (X ³ ) X ⁴ in which X ³ and X ⁴ independently represent adamantyl. More preferably, if X ¹ represents the same adamantyl group as X ³ , X ² represents the same adamantyl group as X ⁴ , and Q ¹ is the same as Q ² .

Preferably, when the compound of formula IIIa is HQ ² (X ¹ ) X ² in which X ¹ and X ^{2 are} independently congressyl, then the compound of formula IIIb is HQ ¹ (X ³ ) X ⁴ in which X ³ and X ⁴ independently represent congressyl. More preferably, X ¹ represents the same congressive group as X ³ , X ² represents the same congressive group as X ⁴ , and Q ¹ is the same as Q ² .

Preferably, when the compound of formula IIIa is HQ ² (X ¹ ) X ² in which X ¹ and X ² together with Q ² to which they are attached form a 2-phospha-adamantyl group, then the compound of formula IIIb is HQ ¹ (X ³ ) X ⁴ in which X ³ and X ⁴ together with Q ¹ to which they are attached form a 2-phosphaadamantyl group. More preferably, X ¹ and X ² together with Q ² form the same 2-phosphaadamantyl group formed by combining X ³ and X ⁴ together with Q ¹ .

Preferably, when the compound of formula IIIa is HQ ² (X ¹ ) X ² in which X ¹ and X ² together with Q ² to which they are attached form a cyclic system of formula Ia, then the compound of formula IIIb is HQ ¹ (X ³ ) X ⁴ in which X ³ and X ^4, together with Q ¹ to which they are attached, form a cyclic system of formula Ib. Preferably, if the cyclic system of formula Ia is the same as the cyclic system of formula Ib.

Most preferably, when the compound of formula IIIa is identical to the compound of formula IIIb.

A compound of formula II wherein LG ₂ is hydroxyl or NR ²³ R ²⁴ can be prepared by reacting a compound of formula IV in which A ₁ , LG ₁ , K, D, E, M, L ₁ , L ₂ , n and m are the same as indicated for the compounds of formula II, and Li is lithium,

with a compound of formula Va,

in which A ₂ is the same as indicated for the compound of formula II, and LG ₂ is oxygen (thus forming a hydroxyl derivative in the subsequent reaction with compound IV) or NR ²³ R ²⁴ . Preferably, when in the compound of formula Va, A ₂ is methylene and LG ₂ is NMe ₂ . For example, a compound of formula Va may be an Eschenmoser salt of I ^- CH ₂ N ⁺ Me ₂ (see Glidewell C, Journal of Organometallic Chemistry, 527, (1997), pp. 259-261).

Alternatively, in the compound of formula Va, A ₂ is methylene and LG ₂ is oxygen. For example, a compound of formula Va may be formaldehyde, which for practical purposes may be in the form of paraformaldehyde.

The reaction can be carried out using methods that are well known to specialists in this field. For example, the reaction can be performed by stirring a solution of the compound of formulas IV and Va in an appropriate solvent, such as diethyl ether, at room temperature.

Preferably, in the compound of formula IV, LG _{1 is} not hydroxyl, since the hydroxyl function should generally be protected before ortho-lithiation of the precursor compound (compound VI below) into the compound of formula IV. Preferably, in the compound of formula IV, LG ₁ is NR ²³ R ²⁴ , most preferably LG ₁ is NMe ₂ .

A compound of formula IV can be prepared by ortholitizing a compound of formula VI in which A ₁ , LG ₁ , K, D, E, M, L ₁ , L ₂ , n and m are the same as indicated for the compound of formula IV,

by reaction with alkyl lithium (e.g. n-butyl lithium). Preferably, when in the compound of formula VI, LG _{1 is} not hydroxyl, since the hydroxyl functionality should generally be protected before carrying out the ortho-lithiation reaction. Preferably, in the compound of formula VI, LG ₁ is NR ²³ R ²⁴ , most preferably LG ₁ is NMe ₂ .

Typically, the ortho-lithiation reaction of a compound of formula VI with alkyl lithium is carried out in an inert solvent, for example tetrahydrofuran or hexane, at low temperatures (for example, -78 ° C) in a nitrogen atmosphere.

The compound of formula VI, where LG ₁ is hydroxyl or NR ²³ R ²⁴ , can be obtained from the compounds of formula VII, in which K, D, E, M, L ₁ , L ₂ , n and m are the same as indicated for the compound formula VI, and Li is lithium

reaction with a compound of formula Vb,

in which A ₁ is the same as indicated for the compound of formula VI, and LG ₁ is oxygen (thereby forming a hydroxyl derivative in the subsequent reaction with compound VII) or NR ²³ R ²⁴ . Preferably, LG ₁ is NR ²³ R ²⁴ , in particular NMe ₂ . In other words, the compound of formula Vb is preferably a Eschenmozar salt. The reaction can be carried out using the same conditions as described above to obtain the compound of formula II.

Similarly, a compound of formula VII can be obtained by lithiation of a compound of formula VIII,

in which K, D, E, M, L ₁ , L ₂ , n and m are the same as indicated for the compounds of formula VII.

In a suitable case, a compound of formula I in which K is —A ₃ —Q ³ (X ⁵ ) X ⁶ can be prepared from a compound of formula IX in which A ₁ , A ₂ , A ₃ , D, E, M, L ₁ , L ₂ , n and m are the same as indicated for the compounds of formula I, and LG ₁ , LG ₂ and LG ₃ are suitable leaving groups, as defined herein,

a reaction with a compound of formula IIIa and IIIb as defined herein and a compound of formula IIIc,

in which X ⁵ represents CR ¹³ (R ¹⁴ ) (R ¹⁵ ), congressyl or adamantyl, X ⁶ represents CR ¹⁶ (R ¹⁷ ) (R ¹⁸ ), congressil or adamantyl, or X ⁵ and X ⁶ together with Q ³ form a 2-phospha-adamantyl group, or X ⁵ and X ⁶ together with Q ³ to which they are attached form a cyclic system of the formula Ic; and R ¹³ to R ¹⁸ , congressyl, adamantyl, Q ³ , 2-phospha-adamantyl and the cyclic system of formula Ic are the same as indicated for the compound of formula I.

Preferably, when the compound of formula IIIa is HQ ² (CR ¹ (R ² ) (R ³ )) CR ⁴ (R ⁵ ) (R ⁶ ), then the compound of formula IIIb is HQ ¹ (CR ⁷ (R ⁸ ) (R ⁹ )) CR ¹⁰ (R ¹¹ ) (R ¹² ) and the compound of formula IIIc is HQ ³ (CR ¹³ (R ¹⁴ ) (R ¹⁵ )) CR ¹⁷ (R ¹⁸ ) (R ¹⁹ ), in which Q ^{1 is} the same that Q ² and Q ³ , R ^{1 is} the same as R ⁷ and R ¹³ , R ^{2 is} the same as R ⁸ and R ¹⁴ , R ^{3 is} the same as R ⁹ and R ¹⁵ , R ^{4 is} the same R ¹⁰ and R ¹⁶ , R ^{5 is} the same as R ¹¹ and R ¹⁷ , and R ^{6 is} the same as R ¹² and R ¹⁸ .

Preferably, when X ¹ and X ² in the compound of formula IIIa are independently adamantyl, then X ³ and X ⁴ in the compound of formula IIIb are independently adamantyl, and X ⁵ and X ⁶ in the compound of formula IIIc are independently adamantyl. Most preferably, X ¹ to X ⁶ are the same adamantyl group.

Preferably, when X ¹ and X ² in the compound of formula IIIa are independently congressyl, then X ³ and X ⁴ in the compound of formula IIIb are independently congressyl, and X ⁵ and X ⁶ in the compound of formula IIIc are independently congressyl. Most preferably, X ¹ to X ⁶ are the same congressional group.

Preferably, when X ¹ and X ² together with Q ² to which they are attached in the compound of formula IIIa form a 2-phospha-adamantyl group, then X ³ and X ⁴ together with Q ¹ in the compound of formula IIIb, and X ⁵ and X ⁶ together with Q ³ in the compound of formula IIIc in both cases form a 2-phospha-adamantyl group.

Preferably, when X ¹ and X ² together with Q ² to which they are attached form a cyclic system of formula Ia, then X ³ and X ⁴ together with Q ¹ to which they are attached in compound IIIb form a cyclic system of formula Ib, and X ⁵ and X ⁶ together with Q ³ to which they are attached in compound IIIc form a cyclic system of formula Ic.

Most preferably, when the compounds of formula IIIa, IIIb and IIIc are identical.

Suitably, LG ₃ is a leaving group, as defined herein with respect to LG ₁ and LG ₂ . Preferably, LG ₃ is NR ²³ R ²⁴ or hydroxyl. Most preferably, LG ₃ is NMe ₂ , in particular when both LG ₁ and LG _{2 are} also NMe ₂ .

Similarly, a compound of formula IX in which LG ₃ is hydroxyl or NR ²³ R ²⁴ can be obtained by ortho-lithiation of a compound of formula II in which A ₁ , A ₂ , LG _1, LG ₂ , D, E, M, L ₁ , L ₂ , n and m are the same as defined herein for a compound of formula II, and K is hydrogen, followed by reaction with a compound of formula Vc,

in which A _{3 is} defined as indicated for the compound of formula IX, and LG ₃ is oxygen or NR ²³ R ²⁴ . Preferably, when a compound of formula II is used to synthesize a compound of formula IX, then LG ₁ and LG _{2 are} not hydroxyl, since the hydroxyl function usually needs to be protected before carrying out the ortho-lithiation reaction. Preferably, when both LG ₁ and LG ₂ are NR ²³ R ²⁴ , most preferably, when both LG ₁ and LG ₂ are NMe ₂ .

Similarly, a compound of formula I in which K is —A ₃ —Q ³ (X ⁵ ) X ⁶ and D is —A ₄ —Q ⁴ (X ⁷ ) X ⁸ can be prepared from a compound of formula IX in which A ₁ , A ₂ , A ₃ , LG ₁ , LG ₂ , LG ₃ , E, M, L ₁ , L ₂ , n and m are the same as defined herein for a compound of formula IX, and D is hydrogen, ortho by lithiation and reaction with a compound of formula Vd,

in which A ₄ is the same as defined here for the compound of formula I, and LG ₄ is oxygen or NR ²³ R ²⁴ as defined herein, forming a compound of formula X, followed by reaction of the obtained compound of formula X with derivatives of phosphine, arsine or stilbene formulas IIIa, IIIb, IIIc , as defined herein, and with a compound of formula IIId,

in which X ⁷ represents CR ³¹ (R ³² ) (R ³³ ), congressyl or adamantyl, X ⁸ represents CR ³⁴ (R ³⁵ ) (R ³⁶ ), congressil or adamantyl, or X ⁷ and X ⁸ together with Q ⁴ form a 2-phospha-adamantyl group, or X ⁷ and X ⁸ together with Q ⁴ form a cyclic system of formula Id, and groups R ³¹ to R ³⁶ , adamantyl, Q ⁴ , 2-phospha-adamantyl and a cyclic system of formula Id are defined as described for formulas I.

Preferably, when the compound of formula IIIa is HQ ² (CR ¹ (R ² ) (R ³ )) CR ⁴ (R ⁵ ) (R ⁶ ), then the compound of formula IIIb is HQ ¹ (CR ⁷ (R ⁸ ) (R ⁹ )) CR ¹⁰ (R ¹¹ ) (R ¹² ), the compound of formula IIIc is HQ ³ (CR ¹³ (R ¹⁴ ) (R ¹⁵ )) CR ¹⁶ (R ¹⁷ ) (R ¹⁸ ) and the compound of formula IIId is HQ ⁴ (CR ³¹ (R ³² ) (R ³³ )) CR ³⁴ (R ³⁵ ) (R ³⁶ ), and Q ¹ is the same as Q ² , Q ³ and Q ⁴ , R ¹ is the same as R ⁷ , R ¹³ and R ³¹ , R ² is the same as R ⁸ , R ¹⁴ and R ³² , R ³ is the same as R ⁹ , R ¹⁵ and R ³³ , R ⁴ is the same as R ¹⁰ , R ¹⁶ and R ³⁴ , R ⁵ is the same as R ¹¹ , R ¹⁷ and R ³⁵ , and R ⁶ is the same as R ¹² , R ¹⁸ and R ³⁶ .

Preferably, when X ¹ and X ² in the compound of formula IIIa are independently adamantyl, then X ³ and X ⁴ in the compound of formula IIIb are independently adamantyl, X ⁵ and X ⁶ in the compound of formula IIIc are independently adamantyl, and X ⁷ and X ⁸ in the compound of formula IIId are independently adamantyl.

Preferably, when X ¹ and X ² in the compound of formula IIIa are independently congressyl, then X ³ and X ⁴ in the compound of formula IIIb are independently congressyl, X ⁵ and X ⁶ in the compound of formula IIIc are independently congressyl, and X ⁷ and X ⁸ in the compound of formula IIId independently represents congressyl.

Preferably, when X ¹ and X ² together with Q ² to which they are attached in the compound of formula IIIa form a 2-phospha-adamantyl group, then X ³ and X ⁴ together with Q ¹ in the compound of formula IIIb, and X ⁵ and X ⁶ together with Q ³ in the compound of formula IIIc and X ⁷ and X ⁸ together with Q ⁴ in the compound of formula IIId each independently form a 2-phospha-adamantyl group.

Preferably, when X ¹ and X ² together with Q ² to which they are attached in the compound of formula IIIa form a cyclic system of formula Ia, then X ³ and X ⁴ together with Q ¹ in the compound of formula IIIb, X ⁵ and X ⁶ together with Q ³ in the compound of formula IIIc and X ⁷ and X ⁸ together with Q ⁴ in the compound of formula IIId form a cyclic system of the formula Ib, Ic and Id, respectively.

Most preferably, when the compounds of formula IIIa, IIIb, IIIc and IIId are identical.

Suitably, when a 1,2,3,4-substituted derivative of the compound of formula I is obtained, it is preferred that LG ₁ , LG ₂ and LG _{3 the} compounds of formula IX are not hydroxyl and each is NR ²³ R ²⁴ , as herein is defined.

Similarly, a compound of formula I in which K is —A ₃ —Q ³ (X ⁵ ) X ⁶ , D is —A ₄ —Q ⁴ (X ⁷ ) X ^8, and E is —A ₅ —Q ⁵ ( X ⁹ ) X ¹⁰ can be obtained from the compounds of formula XI,

in which A ₁ , A ₂ , A ₃ , LG _1, LG ₂ , LG ₃ , M, L ₁ , L ₂ , n and m are defined as described herein for a compound of formula IX, A _{4 is} defined as described herein for a compound of formula I, LG ₄ represents a leaving group and E represents hydrogen by sequential ortho-lithiation and reaction with a compound of formula V (e),

in which A _{5 is} defined as described herein for a compound of formula I, and LG ₅ is oxygen or NR ²³ R ²⁴ , as defined herein, by subsequent reaction of the obtained compound with phosphine, arsine and stilbene derivatives of formula IIIa, IIIb, IIIc, IIId, as defined here, and formulas IIIe,

in which X ⁹ represents CR ³⁷ (R ³⁸ ) (R ³⁹ ), congressyl or adamantyl, X ¹⁰ represents CR ⁴⁰ (R ⁴¹ ) (R ⁴² ), congressil or adamantyl, or X ⁹ and X ¹⁰ together with Q ⁵ form a 2-phospha-adamantyl group, or X ⁹ and X ¹⁰ together with Q ⁵ form a cyclic system of formula Ie, and groups R ³⁷ to R ⁴² , adamantyl, 2-phospha-adamantyl, Q ⁵ and a cyclic system of formula Ie are the same as defined for the compounds of formula I.

Suitably, when a 1,2,3,4,5-substituted derivative of formula I is obtained, it is preferred that LG ₁ , LG ₂ , LG ₃ and LG _{4 the} compounds of formula X are not hydroxyl and each is NR ²³ R ²⁴ , as defined here.

Preferably, when the compounds of formulas IIIa, IIIb, IIIc, IIId and IIIe are identical.

Compounds of formula IIIa in which X ¹ and X ² together with Q ² to which they are attached form a 2-phospha-adamantyl group can be prepared by methods well known to those skilled in the art. Some 2-phospha-adamantyl compounds are obtained from Cytec Canada Inc of 901 Garner Road, Niagara Falls, Ontario, Canada L2E 6T4. Also, the corresponding 2-phospha-adamantyl compounds of the formulas IIIb, IIIc, IIId and IIIe can be obtained from the same supplier or obtained by similar methods.

Compounds of formula IIIa in which X ¹ and X ² are adamantyl can be prepared by methods well known to those skilled in the art, for example by reacting adamantane (or a substituted derivative thereof, as defined herein) with phosphorus trichloride and aluminum chloride, followed by reduction intermediate derivative (adamantyl) ₂ P (O) Cl. The corresponding compounds of formulas IIIb, IIIc, IIId and IIIe, in which groups X ² to X ¹⁰ , respectively, is adamantyl, can also be obtained by similar methods.

Compounds of formula IIIa in which X ¹ and X ^2, together with Q ² to which they are attached, form a cyclic system of formula Ia, can be prepared by reacting phosphine (PH ₃ ) with a compound of formula XII,

in which Y ¹ and from R ⁴⁹ to R ^{55 are} defined as described herein for a compound of formula I. The corresponding compounds of formulas IIIb, IIIc, IIId and IIIe can be synthesized by similar methods.

In a convenient case, the compound of formula I, in which K, D, E, M, A ₂ , A ₁ , L ₂ , L ₁ , Q ¹ , Q ² , m and n are defined as described here for the compounds of formula I, X ¹ and X ² together with Q ² to which they are attached form a cyclic system of formula Ia, and X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of formula Ib, can be obtained by reacting a compound of formula XV,

in which K, D, E, M, A ₂ , A ₁ , L ₂ , L ₁ , Q ¹ , Q ² , m and n are defined as described herein for a compound of formula I, with a compound of formula XVIa and XVIb,

in which Y ¹ , Y ² , from R ⁴⁹ to R ^{55 are} defined as described herein for a compound of formula I.

Suitably, when the reaction can be completed by heating the reactants at 120 ° C. for about 20 hours.

Thus, according to a fifth aspect, the present invention provides a compound of formula XV, as indicated herein.

Similarly, a compound of formula I in which D, E, M, A ₂ , A ₁ , L ₂ , L ₁ , Q ¹ , Q ² , m and n are defined as described herein for a compound of formula I, X ¹ and X ² together with Q ² to which they are attached form a cyclic system of the formula Ia, X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of the formula Ib, and K represents -A ₃ -Q ³ (X ⁵ ) X ⁶ in which X ⁵ and X ^6, together with Q ³ to which they are attached, form a cyclic system Ic and A _{3 are} defined as described herein for a compound of formula I, can be obtained by reacting a compound of formula XVII,

in which D, E, M, A ₂ , A ₁ , L ₂ , L ₁ , Q ¹ , Q ² , Q ³ , m and n are defined as described herein for a compound of formula I, with a compound of formulas XVIa, XVIb, XVIc .

in which Y ¹ , Y ² , Y ³ , from R ⁴⁹ to R ^{55 are} defined as described herein for a compound of formula I.

Preferably, when Y ¹ is the same as Y ² and Y ³ in the compound of the formula XVIa, XVIb and XVIc. Most preferably, when the compounds of formulas XVIa, XVIb and XVIc are identical.

In a suitable case, when the compound of formula XV can be obtained from the compounds of formula XVIII, in which K, D, E, M, L ₂ , L ₁ , A ₁ , A ₂ , Q ¹ , Q ² , n and m are defined as here indicated for the compounds of formula XV, by reduction, for example, with sodium metabisulfite.

Suitably, a compound of formula XVIII can be prepared from a compound of formula XIX, wherein K, D, E, M, A ₂ , A ₁ , L ₂ , L ₁ , m and n are defined as described herein for a compound of formula XVIII,

reacting with an alkyl iodide such as methyl iodide to form a 1,2-dimethyl iodide salt derived from a compound of formula XIX, and then reacting with trihydroxymethylphosphine / stilbene / arsine.

Specialists in this field should take into account that 1,2,3,4- and 1,2,3,4,5-substituted compounds can be obtained in similar ways.

Compounds of formulas IIIa, IIIb, IIIc, IIId, IIIe, Va, Vb, Vc, Vd, Ve, VIII, XV, XVIa, XVIb, XVIc, XVII, XIX and their derivatives, which are neither commercially available nor described later here can be obtained using conventional synthesis techniques in accordance with standard textbooks on organic chemistry or with the previous literature, from readily available starting materials using appropriate reagents and reaction conditions.

Specialists in this field should take into account that, within the described methods, the order of the used synthesis steps can be changed and will depend on factors such as the nature of other functional groups present in a particular substance, the availability of key intermediates, and strategies for choosing protective groups (if this is the case). It is clear that such factors will also influence the choice of reagent for use in the mentioned synthesis steps.

It should also be taken into account that interconversions and transformations of various standard substituents or functional groups within certain compounds of formula I will lead to other compounds of formula I.

According to a sixth aspect, the present invention provides a method for carbonylating an ethylenically unsaturated compound, comprising reacting the ethylenically unsaturated compound with carbon monoxide and a co-reagent in the presence of a compound of the present invention.

Suitable co-reagents include compounds containing a nucleophilic component and a mobile hydrogen atom. Thus, the compounds of the present invention can catalyze the reactions of hydroformylation, hydrocarboxylation, hydroesterification and hydroamidation of ethylenically unsaturated compounds.

Preferred co-reagents include molecular hydrogen, water, alcohols, primary or secondary amines or amides such as diethylamine, N, N-dimethylethylenediamine, carboxylic acids, for example acetic acid, propionic acid, trimethylacetic acid and aromatic alcohols.

Preferably, the co-reagent has a hydroxyl functional group or is molecular hydrogen. Hydroxyl-containing compounds may be branched or linear and contain alcohols, in particular C ₁ -C ₃₀ alcohols, such as neopentyl alcohol, ethyl hexyl alcohol, tert-amyl alcohol, include aromatic alcohols, which may optionally be substituted with one or more substituents, selected from lower alkyl, aryl, hetero, halogen, cyano, nitro, OR ¹⁹ , OC (O) R ²⁰ , C (O) R ²¹ , C (O) OR ²² , NR ²³ R ²⁴ , C (O) NR ²⁵ R ²⁶ , C (S) R ²⁷ R ²⁸ , SR ²⁹ or C (O) SR ³⁰ , as indicated here. Particularly preferred C ₁ -C ₈ alcohols, such as methanol, ethanol, propanol, isopropanol, isobutanol, tert-butyl alcohol, n-butanol, octanol, phenol and chlorocaprylic alcohol. Although monobasic alcohols are most preferred, polyalkanols are also suitable, preferably selected from those from diols to octanols, such as diols, triols, tetraols and sugars. Typically, such polyalkanols are selected from 1,2-ethanediol, 1,3-propanediol, glycerol, 1,2,4-butanetriol, 2- (hydroxymethyl) -1,3-propanediol, 1,2,6-trihydroxyhexane, pentaerythritol, 1 1,1-tri (hydroxymethyl) ethane, mannose, sorbose, galactose and other sugars. Preferred sugars include sucrose, fructose and glucose. Particularly preferred alcohols are methanol and ethanol.

The amount of alcohol is not critical. Typically, an excess amount of alcohol is used compared to the amount of ethylene unsaturated compound to be carbonylated. Therefore, alcohol can be used in the reaction as a solvent, although other solvents can also be used if desired.

It will be appreciated that the final reaction product is determined, at least in part, by the source of the compound used as a co-agent. If water is used as a compound containing a hydroxyl group, the final product is the corresponding carboxylic acid, while the corresponding ester is formed using alcohol.

Preferably, the ethylene unsaturated compound comprises from 2 to 20 carbon atoms. More preferably, when the ethylene unsaturated compound contains from 2 to 14 carbon atoms.

Suitably, the ethylene unsaturated compound may include more than one carbon-carbon double bond, where the double bonds are conjugated or non-conjugated.

Preferably, when the ethylene unsaturated compound has from 1 to 3 carbon-carbon double bonds per molecule, in particular from 1 to 2 carbon-carbon double bonds, mainly only one carbon-carbon double bond per molecule.

Unless specifically indicated, an ethylenically unsaturated compound may, when there is a sufficient number of carbon atoms, be linear or branched, cyclic, acyclic or partially cyclic / acyclic, and / or may be substituted or limited by one or more substituents selected from lower alkyl, aryl, alkylaryl, hetero, alkyl hetero, halogen, OR ¹⁹ , OC (O) R ²⁰ , C (O) R ²¹ , C (O) OR ²² , NR ²³ R ²⁴ , C (O) NR ²⁵ R ²⁶ , NO ₂ , CN, SR ²⁷ , in which from R ¹⁹ to R ²⁷ each independently represent hydrogen or lower alkyl. Substituted olefins include styrenes and unsaturated carboxylic acid alkyl esters such as methacrylates. Accordingly, ethylenically unsaturated compounds may exhibit cis (E) and trans (Z) isomerism.

Examples of suitable ethylenically unsaturated compounds having 2 or more carbon atoms include ethene, propene, but-1-ene, but-2-ene, isobutene, pentene, hexene, octene, dodecene , 1,5-cyclooctadiene , cyclododecene, methylpentenoate , pentenoic acid nitrile, 1,3-butadiene, 1,3-pentadiene, vinyl acetate and 1,3-hexadiene. Particularly preferred ethylenically unsaturated compounds include ethene, oct-1-ene, vinyl acetate and 1,3-butadiene, in particular ethene.

The method according to the invention can have the greatest advantages in carbonylation of ethylenically unsaturated compounds which are internally unsaturated, such as but-2-ene, pent-2-ennitrile, oct-2-ene, oct-3-ene, oct-4-ene or methylpent-3-enoate. For these compounds, side chain reactions proceed more easily and it may be more difficult to obtain linear products. In a convenient case, the compounds of this invention can exhibit high regioselectivity with respect to the linear product of the subsequent carbonylation of internally unsaturated ethylene compounds.

Preferably, when the carbonylation is carried out at a temperature of from 0 to 250 ° C, more preferably from 40 to 150 ° C, most preferably from 70 to 120 ° C.

Suitably, the carbonylation reaction is carried out at a pressure of at least atmospheric pressure. Preferably, the carbonylation reaction is carried out at a total pressure greater than or equal to 1 × 10 ⁵ Pa, more preferably at a pressure greater than or equal to 5 × 10 ⁵ Pa, most preferably at a pressure greater than or equal to 10 × 10 ⁵ Pa. Preferably, the carbonylation reaction is carried out at a total pressure of less than or equal to 100 × 10 ⁵ Pa, more preferably at a pressure less than or equal to 65 × 10 ⁵ Pa, most preferably at a pressure less than or equal to 50 × 10 ⁵ Pa.

A partial pressure of carbon monoxide in the range from 1 to 65, in particular from 5 to 50 × 10 ⁵ Pa, is preferred. In the method of this invention, carbon monoxide can be used in pure form either with a dilute inert gas such as nitrogen or carbon dioxide, or with a noble gas such as argon. Small amounts of hydrogen may also be present, usually less than 5 vol.%.

The ratio (volume / volume) of the ethylenically unsaturated compound and the compound containing the co-reagent can vary widely and is usually in the range from 1: 0.1 to 1:10, preferably from 2: 1 to 1: 2.

The amount of catalyst of the invention used in the carbonylation reaction of an ethylenically unsaturated compound is not critical. Good results can be obtained by using from 10 ^-7 to 10 ^-1 mol, more preferably from 10 ^-6 to 10 ^-2 mol of Group VIIIB metals or their compounds (as indicated in (a) here) per mole of ethylene unsaturated compound.

Preferably, as mentioned here, the reaction is carried out by adding a source of anions, as defined here, in addition to the compounds of the invention. Suitably, the source of anions may be added to the carbonylation reaction separately from the compounds of the invention. Preferably, as mentioned here, when the compounds of the invention include a source of anions. In a suitable case, the molar ratio of anions to Group VIIIB metals in the compounds of the invention when used for carbonylation of ethylenically unsaturated compounds is within wide limits and, in a suitable case, it is in the range from 2: 1 to 2000: 1, preferably from 10: 1 to 200: one.

Suitably, the carbonylation of an ethylenically unsaturated compound, as defined herein, may be carried out in one or more aprotic solvents. Suitable solvents include ketones, such as, for example, methylbutyl ketone; ethers, such as, for example, anisole (methylphenyl ether), 2,5,8-trioxanonan (diglyme), diethyl ether, tetrahydrofuran, diphenyl ether, diisopropyl ether and diethylene glycol dimethyl ether; esters such as, for example, methyl acetate, dimethyl adipate and butyrolactone; amides, such as, for example, dimethylacetamide and N-methylpyrrolidone; and sulfoxides and sulfones, such as, for example, dimethyl sulfoxide, diisopropyl sulfone, sulfolane (tetrahydrothiophene-2,2-dioxide), 2-methylsulfolane and 2-methyl-4-ethylsulfolane.

Aprotic solvents having a dielectric constant with a value less than 50 are very suitable; values in the range from 3 to 8, at 298.15 K and 1 × 10 ⁵ Pa are more preferred. In this context, the dielectric constant for a given solvent is used in its normal value, representing the ratio of the electric capacitance of a capacitor with a given substance as a dielectric to the electric capacitance of the same capacitor with a vacuum as a dielectric. The values of dielectric constants of common organic liquids can be found in general reference books such as the Handbook of Chemistry and Physics, 76 ^th edition, edited by David R. Lide et al., Published by CRC press in 1995 Mr and usually quoted for a temperature of about 20 ° C or 25 ° C, i.e. about 293.15 K or 298.15 K, and at atmospheric pressure, i.e. about 1 × 10 ⁵ Pa, or can easily be converted for a given temperature and pressure using the quoted conversion factors. If literature data for a particular substance is not available, the dielectric constant can be easily measured using established physicochemical methods.

For example, the dielectric constant of anisole is 4.3 (at 294.2 K), diethyl ether is 4.3 (at 293.2 K), sulfolane is 43.4 (at 303.2 K), methyl pentanoate is 5.0 ( at 293.2 K), diphenyl ether is 3.7 (at 283.2 K), dimethyl adipate is 6.8 (at 293.2 K), tetrohydrofuran is 7.5 (at 295.2 K), methylnonanoate is 3 9 (at 293.2 K). A preferred solvent is anisole.

If the co-reagent is alcohol, an additional preferred aprotic solvent is an ester of the carbonylation product of an ethylene unsaturated compound, carbon monoxide and alcohol.

The reaction is preferably carried out in excess of an aprotic solvent, i.e. in a ratio (v / v) of an aprotic solvent to a compound containing a co-agent of at least 1: 1. Preferably, when this ratio is in the range from 1: 1 to 10: 1, and more preferably from 1: 1 to 5: 1. The most preferred ratio (vol./about.) Is in the range from 1.5: 1 to 3: 1.

The catalyst compounds of the present invention can act as a “heterogeneous” catalyst or as a “homogeneous” catalyst.

By the term “homogeneous” catalyst is meant a catalyst, i.e. a compound of the invention that does not have a carrier but is simply added or formed during the reaction from carbonylation reaction reagents (i.e., ethylene unsaturated compound, hydroxyl-containing compound and carbon monoxide), preferably in a suitable solvent, as described herein.

The term “heterogeneous” catalyst is understood to mean a catalyst, i.e. a compound of the invention that is on a carrier.

Thus, according to a seventh aspect, the present invention provides a catalyst system comprising a carrier, preferably an insoluble carrier, and a compound of the invention as defined herein. Conveniently, the use of an insoluble carrier makes it easy to separate the catalyst, for example by filtration, from the reaction mixture.

Preferably, the carrier comprises a polymer such as a polyolefin, polystyrene or a polystyrene / divinylbenzene copolymer; silicon derivatives such as functionalized silicon dioxide, silicone or silicone rubber; or other porous particulate materials such as, for example, inorganic oxides or inorganic chlorides such as alumina and montmorillomite.

Preferably, the support material is porous silica, which has a surface area of 10 to 700 m ² / g, and the total pore volume is in the range of 0.1 to 4.0 cm ³ / g and the average particle size is in the range of 10 up to 500 microns. More preferably, when the surface area is in the range of 50 to 500 m ² / g, the pore volume is in the range of 0.5 to 2.5 cm ³ / g and the average particle size is in the range of 20 to 200 μm. Most preferably, if the surface area is in the range of 100 to 400 m ² / g, the pore volume is in the range of 0.8 to 3.0 cm ³ / g and the average particle size is in the range of 30 to 100 μm. The average pore size of the material of a typical porous carrier is in the range from 10 to 1000 Å. Preferably, when the average pore diameter of the material used is in the range from 50 to 500 U, and most preferably from 75 to 350 E. In particular, it is desirable to dehydrate silica at a temperature of from 100 to 800 ° C. for about 3 to 24 hours.

The carrier may suitably be an elastic or rigid material, the insoluble carrier is coated and / or impregnated with the compound of the invention using techniques well known to those skilled in the art. Alternatively, when the compound of the invention is fixed to the surface of an insoluble carrier, optionally via a covalent bond, and optionally includes a difunctional cleavage molecule to separate the compound from the insoluble carrier.

The compound of the invention can be fixed to the surface of an insoluble carrier by initiating a reaction of a functional group present in a compound of formula I, for example, a ligand substituent L ₁ or a substituent K, D, and E of the cyclopentadienyl component, with a suitable reactive group present on the carrier or previously applied to the carrier. The combination of a reactive group with a suitable substituent of the compound of the invention provides the formation of a heterogeneous catalyst in which the compound of the invention and the carrier are linked via a bond, such as an ester group, an ester group, an amido, amino, urea, or keto group.

The choice of reaction conditions in order to bind the compound of the present invention to a carrier depends on the nature of the substituent (s) of the compound and the nature of the groups of the carrier. For example, reagents such as carbodiimides, 1,1'-carbonyldiimidazole, and methods such as the use of mixed anhydrides and reductive amination can be used.

According to an eighth aspect, the present invention provides the use of a compound of the invention or a compound of the invention, supported on a carrier, as a catalyst.

It will be appreciated that any of a number of features presented in the first aspect of the invention may be considered as a preferred feature of the second, third, fourth, fifth, sixth, seventh and eighth aspects of the present invention and vice versa.

The invention will now be described using the following non-limiting examples.

Example 1

Obtaining 1,2-bis (dimethylaminomethyl) ferrocene

N-butyllithium (Aldrich, 2.5 molar solution in hexane, 24 ml, 54 mmol) was added to a solution of (dimethylaminomethyl) ferrocene (Aldrich, 13.13 g, 10.69 ml, 48.97 mmol) in diethyl ether (80 ml) in an atmosphere of nitrogen at a temperature of 25 ° C and the reaction mixture was stirred for 4 hours. The resulting red solution was then cooled to approximately −70 ° C. in a dry ice / acetone bath and Eschenmozer salt (ICH ₂ NMe ₂ ) (Aldrich, 10 g, 54 mmol) was added. The reaction mixture was allowed to warm to room temperature and was left stirring overnight.

The resulting solution was quenched with excess sodium hydroxide and the resulting product was extracted with diethyl ether (3 × 80 ml), dried over anhydrous magnesium sulfate, filtered over celite and the volatile impurities were removed in vacuo to give the crude title compound as a pale orange crystalline solid. The crude product was recrystallized from a light gasoline fraction, cooling to -17 ° C, and the recrystallized product was washed with cold gasoline to give the title compound as a light orange solid (13.2 g, 74%). The compound may be further purified by distillation to give 8.5 g (52%) of the title compound (mp 74 ° C).

¹ H NMR (250 MHz; CDCl ₃ ): δ 4.23 (brd, 2H), 4.11-4.10 (t, 1H), 4.04 (s, 5H), 3.43, 3 38, 3.23, 3.18 (AB quartet, 2H); 2.22 (s, 6H).

¹³ C NMR (63 MHz; CDCl ₃ ): δ 83.81, 70.40, 69.25, 66.84, 57.35, 45.23.

Elemental analysis: Found: C 63.7%; H 8.9%; N 9.5%

Calculated: C 64.0%; H 8.1%; N 9.4%

Example 2

Obtaining 1,2-bis (di-tert-butylphosphinomethyl) ferrocene

Di-tert-butylphosphine (Aldrich, 0.616 ml, 3.33 mmol) was added to a solution of 1,2-bis (dimethylaminomethyl) ferrocene (Example 1, 0.5 g, 1.66 mmol) in anhydrous acetic acid (100 ml) under nitrogen atmosphere and the resulting mixture was stirred at 80 ° C for 72 hours. Anhydrous acetic acid was removed in vacuo at approximately 70 ° C. and the crude title product was obtained as an orange-yellow solid. The crude product was recrystallized from ethanol while cooling to -17 ° C, filtered and washed with cold ethanol to give the title compound as a pale yellow solid (0.365 g, 44%, 84 ° C).

¹ H NMR (250 MHz; CDCl ₃ ): δ 4.4 (2H, d, J = 2 Hz), 3.95 (5H, s), 3.75 (1H, t, 2 Hz), 2.8 (2H, dd, 12 Hz, 2 Hz), 2.6 (2H, dd, 12 Hz, 2 Hz), 1.1 (36H, m).

¹³ C NMR (63 MHz; CDCl ₃ ): δ 86.73 (d, 5.46 Hz), 70.08 (d, 4.41 Hz), 69.4665 (s), 63.75 (s), 31.80 (d, 2 Hz), 31.45 (d, 1.98 Hz), 29.89 (d, 1.88 Hz).

³¹ P NMR (101 MHz; CDCl ₃ ): δ 15.00 ppm.

Elemental analysis: Found: C: 66.79%; H: 9.57%

Calculated: C: 66.93%; H: 9.63%

Example 3

Preparation of 1-hydroxymethyl-2-dimethylaminomethylferrocene

N-butyllithium (Aldrich, 1.6 molar solution in diethyl ether, 5.14 ml, 8.24 mmol) was added to a solution of 1-dimethylaminomethylferrocene (Aldrich, 1.0 g, 4.12 mmol) in diethyl ether (20 ml ) in an argon atmosphere. The reaction mixture was stirred for 3 hours and a reddish stain appeared. The solution was then cooled in a dry ice / acetone bath, calcined paraformaldehyde (0.247 g, 2-fold excess) was added, and the resulting mixture was stirred overnight at room temperature. The reaction mixture was then quenched with water, extracted with diethyl ether, dried over MgSO _4, and filtered over celite. The solvent was removed in vacuo to give the crude title compound. The crude product was applied to a column of neutral alumina, which was eluted with a mixture of petroleum ether / diethyl ether (9: 1 ratio) to remove the starting 1-dimethylaminomethylferrocene. The column was then eluted with essentially pure ethyl acetate to isolate the title compound. Ethyl acetate was removed in vacuo to afford the title compound as an orange oily / crystalline solid.

¹ H NMR (250 MHz; CDCl ₃ ): δ 2.131 (s, 6H), 2.735 (d, 1H, 12.512 Hz), 3.853 (d, 1H, 12.512 Hz), 3.984 (dd, 1H, 2.156 Hz), 4.035 (s, 5H), 4.060 (dd, 1H, 2.136 Hz), 4.071 (d, 1H, 12.207 Hz), 4.154 (m, 1H), 4.73 (d, 1H, 12.207 Hz).

¹³ C NMR (61 MHz; CDCl ₃ ): δ 7.688, 84.519, 70.615, 68.871, 68.447, 65.369, 60.077, 58.318, 44.414.

COZY 2D ¹ H NMR

Partially hidden doublet confirmed at 4.071 ppm. and its conjugation with a doublet of 4.73 ppm

Infrared Spectrum (CHCl ₃ ) (SA 0.06 g / 0.8 ml)

2953.8, 2860.6, 2826.0 ¹ , 2783.4, 1104.9 cm ^-1 .

Example 4

Obtaining 1,2-bis (di-tert-butylphosphinomethyl) ferrocene

Di-tert-butylphosphine (Aldrich, 0.54 ml, 2.93 mmol) was added to a solution of 1-hydroxymethyl-2-dimethylaminomethylferrocene (example 3, 0.2 g, 0.753 mmol) in anhydrous acetic acid (15 ml) and acetic acid anhydride (0.753 mmol) in argon atmosphere and the resulting mixture was stirred at 80 ° C for 72 hours. Anhydrous acetic acid was removed in vacuo at approximately 70 ° C. and the crude title product was obtained as an orange-yellow solid. The crude product was recrystallized from ethanol while cooling to -17 ° C, filtered off, washed with cold ethanol to give the title compound as an orange solid (0.23 g).

¹ H NMR (250 MHz; CDCl _3): δ 4,351 (d, 2H, 2 Hz), 4.022 (s, 5H), 3,827 (t, 1H, 2 Hz), 2.858 (ddd, 2H, J _HH 15.869 Hz, J _HP1 3,320 Hz, J _HR2 1,831 Hz), 2.679 (dd, 2H, J _HH 15.869 Hz, J _HP 2.441 Hz), 1.166 (d, 18H, 12,817 Hz), 1.123 (d, 18H, 12,512 Hz).

Fourier-IR (chloroform, NaCl plates)

1104.1, 2863, 2896.0, 2940.0, 2951.8 cm ^-1 .

³¹ P NMR (101 MHz; CDCl ₃ ): δ 15.00 ppm.

Elemental analysis: Found: C: 66.5%; N: 9.6%

Calculated: C: 66.9%; N: 9.6%

Example 5

Preparation of 1-hydroxymethyl-2,3-bis (dimethylaminomethyl) -ferrocene

To a stirred solution of 1,2-bis (dimethylaminomethyl) -ferrocene (Example 1, 0.70 g, 2.32 mmol) in diethyl ether (15 cm ³ ) in an argon atmosphere was added 1.2 equivalents of n-butyllithium (Aldrich, 1 , 75 ml, 1.6 M solution in diethyl ether), the mixture was stirred for three hours to obtain a red solution. The reaction mixture was cooled in a dry ice / acetone bath, calcined paraformaldehyde was added in excess of 2: 1, and the resulting mixture was stirred at room temperature overnight. The mixture was quenched with water and extracted with diethyl ether. The ether extracts were dried over MgSO ₄ , filtered over celite and the solvent was removed in vacuo to give the title compound (0.7 g, 2.12 mmol, 91%) as an orange oil, which partially crystallized upon cooling.

¹ H NMR (250 MHz; CDCl ₃ ): δ 2.133 (s, 6H), 2.171 (s, 6H), 2.910 (d, 1H, 12.817 Hz), 2.998 (d, 1H, 12.512 Hz), 3.425 (d, 1H, 12.817 Hz), 3.812 (d, 1H, 12.512 Hz), 3.962 (s, 5H), 3.99 (d, 1H, 12.207 Hz) (partially hidden by a large cp-ring peak at δ 3.962), 4.068 (d , 1H, 2.136 Hz), 4.125 (d, 1H, 2.136 Hz), 4.747 (d, 1H, 12.207 Hz).

¹³ C NMR (60 MHz; CDCl ₃ ): δ 44.529, 45.244, 55.798, 57.906, 60.271, 67.944, 68.277, 69.612, 84.850, 88.322.

Infrared spectrum (CDCl ₃ / thin film, NaCl plates)

3380.6 (broad), 2955.7 (m), 2862.6, 2825.9 (m), 2774.3 (m), 1353.5 (m), 1104.9 (m), 1038.9 (m), 1006.8 (s) cm ^-1 .

Elemental analysis: Found: C: 62.3%; H: 7.8%; N: 8.8%

Calculated: C: 61.8%; H: 7.9%; N: 8.5%

Example 6

Preparation of 1,2,3-tris (di-tert-butylphosphinomethyl) ferrocene

Di-tert-butylphosphine (Aldrich, 2.60 ml, 13.98 mmol) and acetic anhydride (0.24 ml, 2.33 mmol) were added to a solution of 1-hydroxymethyl-2,3-bis (dimethylaminomethyl) ferrocene (example 5, 0.70 g, 2.12 mmol) in acetic acid (freshly distilled from acetic anhydride 25 cm ³ ), in an argon atmosphere. Then the solution was stirred at 80 ° C for 7 days, the solution during this time acquired a dark orange color. The solvent was removed in vacuo and recrystallized from boiling ethanol, followed by cooling to -17 ° C overnight to obtain the title compound (0.43 g, 0.7 mmol, 31%) as a yellow-orange powder.

¹ H NMR (250 MHz, CDCl ₃ ): δ 1.12 (dd - pseudo triplet, 36H, 12.1 Hz), 1.26 (d, 18H, 10.7 Hz), 2.68 (d, 2H , 17.7 Hz), 2.95 (s, 2H), 3.07 (m, 2H), 4.01 (s, 5H), 4.33 (s, 2H).

Infrared spectrum (CHCl ₃ / thin film, NaCl plates)

1365.5, 1470.3, 2357.1, 2862.8, 2896.7, 2939.1 cm ^-1 .

Example 7

Obtaining 1,2-bis (dicyclohexylphosphinomethyl) ferrocene

The title compound was prepared following the procedure of Example 2 from dicyclohexylphosphine (Strem of 48 High Street Orwell, Royston, United Kingdom SG8 5QW, 659 mg, 3.33 mmol), 1,2-bis (dimethylaminomethyl) ferrocene (0.5 g, 1.66 mmol) and anhydrous acetic acid (100 ml). Yield 0.421 g.

Example 8

Obtaining 1,2-bis (diisobutylphosphinomethyl) ferrocene

The title compound was prepared following the procedure of Example 2 from diisobutylphosphine (Strem 486 mg, 3.33 mmol), 1,2-bis (dimethylaminomethyl) ferrocene (0.5 g, 1.66 mmol) and anhydrous acetic acid (100 ml). Yield 0.372 g.

Example 9

Obtaining 1,2-bis (dicyclopentylphosphinomethyl) ferrocene

The title compound was prepared following the procedure of Example 2 from dicyclopentylphosphine (Strem 566 mg, 3.33 mmol), 1,2-bis (dimethylaminomethyl) ferrocene (0.5 g, 1.66 mmol) and anhydrous acetic acid (100 ml). Yield 0.432 g.

Example 10

Obtaining 1,2-bis (diethylphosphinomethyl) ferrocene

The title compound was prepared following the procedure of Example 2 from diethylphosphine (Strem 299 mg, 3.33 mmol), 1,2-bis (dimethylaminomethyl) ferrocene (0.5 g, 1.66 mmol) and anhydrous acetic acid (100 ml). Yield 0.254 g.

Example 11

Obtaining 1,2-bis (diisopropylphosphinomethyl) ferrocene

The title compound was prepared following the procedure of Example 2 from diisopropylphosphine (Digital Specialty Chemicals 392 mg, 3.33 mmol), 1,2-bis (dimethylaminomethyl) ferrocene (0.5 g, 1.66 mmol) and anhydrous acetic acid (100 ml). Yield 0.262 g.

Example 12

Obtaining 1,2-bis (dimethylphosphinomethyl) ferrocene

The title compound was prepared following the procedure of Example 2 from dimethylphosphine (Digital Specialty Chemicals 206 mg, 3.33 mmol), 1,2-bis (dimethylaminomethyl) ferrocene (0.5 g, 1.66 mmol) and anhydrous acetic acid (100 ml). Yield 0.285 g.

Example 13

Preparation of 1,2-bis (diadamantylphosphinomethyl) ferrocene bismethanesulfonate

Diadamantylphosphine (obtained using the methodology of JR Goerlich, R. Schmutzler; Phosphorus Sulfur and Silicon; 1995, 102, 211-215, 20.0 g, 0.066 mol) was added to a solution of 1,2-bis (dimethylaminomethyl) ferrocene (example 1, 10 g, 0.033 mol) in anhydrous acetic acid (100 ml) in a nitrogen atmosphere and the resulting mixture was stirred at 80 ° C for 72 hours. The resulting orange-yellow precipitate was filtered off and dried in vacuo at approximately 70 ° C to afford the title compound as an orange-yellow solid. The title compound is insoluble in a number of organic solvents, and for this reason it was purified by conversion to bismethanesulfonate by adding an excess of methanesulfonic acid to the methanol suspension of the crude product. This resulted in the complete dissolution of the product salt, which was isolated by removal of methanol in vacuo, followed by washing with ether and drying to afford the title compound as a pale yellow solid (14.0 g, 54%).

¹ H NMR (250 MHz; CD ₃ CN): δ 4.57 (2H, d, 2 Hz), 4.35 (5H, s), 4.27 (1H, t, 2 Hz), 3.34 ( 4H, broad), 2.6 (6H, broad), 2.35-2.18 (18H, broad), 2.16-2.0 (18H, broad), 1.92-1, 72 (24H, broad).

³¹ P NMR (101 MHz; CD ₃ CN): δ 26.58 ppm.

Elemental analysis: Found: C: 64.15%; H: 7.88%

Calculated: C: 64.29%; H: 7.94%

Example 14

Preparation of 1,2-bis (di-1-adamantylphosphinomethyl) ferrocene bis methanesulfonate

Obtaining this ligand was carried out as follows:

14.1 Receipt (1-Ad) ₂ P (O) Cl

Phosphorus trichloride (83 cm ³ , 0.98 mol) was quickly added via cannula to a mixture of aluminum chloride (25.0 g, 0.19 mol) and adamantane (27.2 g, 0.20 mol) to form a tan suspension . The reaction mixture was heated and refluxed. A yellow-orange suspension formed within 10 minutes. The reaction mixture was refluxed for a total of 6 hours. Excess PCl ₃ was removed by distillation at atmospheric pressure (mp. 75 ° C). Upon cooling to ambient temperature, an orange solid formed. Chloroform (250 cm ³ ) was added to give an orange suspension, which was cooled to 0 ° C. Water (150 cm ³ ) was added slowly: initially, the viscosity of the suspension increased, but with the complete addition of water, the viscosity decreased. From this point on, the reaction mixture was no longer kept in an Ar atmosphere. The suspension was filtered on a Buchner funnel to remove a yellow-orange solid impurity. The filtrate consisted of a two-phase system. The lower phase was separated using a separatory funnel, dried over MgSO ₄ and filtered on a Buchner funnel. Volatile impurities were removed using a rotary evaporator, finally dried in vacuum, obtaining an off-white powder. Yield 35.0 g, 99%. ³¹ P NMR: 85 ppm, 99% purity, molecular weight (MM) = 352.85.

14.2 Receive (1-Ad) ₂ PH

LiAlH ₄ (2.54 g, 67.0 mmol) was added over 90 minutes to a cooled (-10 ° C) solution of (1-Ad) ₂ P (O) Cl (10.00 g, 28.3 mmol) in THF (120 cm ³ ). The reaction mixture was allowed to warm to ambient temperature, then was stirred for 20 hours. The gray suspension was cooled to -10 ° C. HCl (aq. 5 cm ³ conc. HCl in 50 cm ³ degassed water) was slowly added using a syringe (initially very slowly due to the exothermic nature of the reaction) to give a two-phase system with some solid in the lower phase. Additionally, HCl (~ 5 cm ³ conc. HCl) was added to improve layer separation. The upper phase was removed using a flat end cannula, dried over MgSO _4, and filtered through a cannula. Volatile impurities were removed in vacuo to give the product as a white powder isolated in a glove box. Yield 6.00 g, 70%, ³¹ P NMR: 17 ppm, purity 100%, MM = 302.44.

14.3 Preparation of 1,2-bis (di-1-adamantylphosphinomethyl) ferrocene bismethanesulfonate

The title compound was prepared following the procedure of Example 13.

Example 15

Preparation of 1,2-bis (di-1- (3,5-dimethyladamantyl) phosphinomethyl) ferrocene bismethanesulfonate

15.1 Di-1- (3,5-dimethyladamantyl) chlorophosphinate

were obtained following the procedure of Example 14.1 using 1,3-dimethyladamantane 21.7 g (0.132 mol) instead of adamantane and AlCl ₃ (18.5 g, 0.14 mol). Yield 23.5 g, MM: 409.08, ³¹ P NMR: δ 87 ppm. (from).

15.2 Di-1- (3,5-dimethyladamantyl) phosphine

were prepared as in the above Example 14.2 using 25 g of di-1- (3,5-dimethyladamantyl) chlorophosphinate instead of di-1-adamantyl chlorophosphinate. Yield 15.7 g, MM: 358.58, ³¹ P NMR: δ 15.7 ppm. (from).

15.3 1,2-bis (di-1- (3,5-dimethyladamantylphosphinomethyl) ferrocene bismethanesulfonate

The title compound was prepared following the procedure of Example 13 using di-1,2- (3,5-dimethyladamantyl) phosphine (23.69 g, 0.066 mol) instead of diadamantylphosphine. Yield 15 g.

Example 16

Preparation of 1,2-bis (di-1- (4-tert-butyladamantyl) phosphinomethyl) ferrocene bismethanesulfonate

16.1 Di-1- (4-tert-butyladamantyl) chlorophosphinate

obtained as di-1-adamantyl chlorophosphinate in Example 14.1 using 4-tert-butyl adamantane 25.37 g (0.132 mol) instead of adamantine and AlCl ₃ (18.5 g, 0.14 mol). Yield 22.6 g, MM : 464.98. ³¹ P NMR: δ 87 ppm (from).

16.2 Di-1- (4-tert-butyladamantyl) phosphine

obtained as di-1-adamantylphosphine in Example 14.2 using 13.5 g of di-1- (4-tert-butyladamantyl) chlorophosphinate instead of di-1-adamantyl chlorophosphinate. Yield 9.4 g, MM: 414.48. ³¹ P NMR: δ 18.62 ppm (from).

16.3 1,2-bis (di-1- (4-tert-butyladamantyl) phosphinomethyl) ferrocene bismethanesulfonate

The title compound was prepared following the procedure for Example 13 using di-1- (4-tert-butyladamantyl) phosphine (27.39 g, 0.066 mol) instead of diadamantylphosphine. Yield 14.52 g.

Example 17

Preparation of 1,2-bis (1-adamantyl-tert-butylphosphinomethyl) ferrocene bismethanesulfonate

17.1 1-Adamantylphosphonic acid dichloride

This compound was synthesized following the method of Olah et al. (J. Org. Chem. 1990, 55, 1224-1227).

17.2 1-adamantylphosphine

LiAlH ₄ (3.5 g, 74 mmol) was added over 2 hours to a cooled solution (0 ° C) of 1-adamantylphosphonic acid dichloride (15 g, 59 mmol) in THF (250 cm ³ ). The reaction mixture was allowed to warm to ambient temperature and was stirred for 20 hours. The gray suspension was then cooled (0 ° C) and HCl (75 cm ³ , 1 M) was slowly added using a syringe to form a two-phase system with some solid in the lower phase. Then, concentrated HCl (8 cm ³ , 11 M) was added to improve the separation of the two layers. The (upper) THF phase was removed using a cannula and dried over magnesium sulfate. After filtering with a cannula, volatiles were removed in vacuo to give the product.

17.3 1-adamantyl-tert-butylphosphine

n-BuLi (20 cm ³ , 32 mmol, 1.6 M solution) was added over 1 hour to a cooled solution of 1-adamantylphosphine (5.0 g, 30 mmol) in THF (100 cm ³ ). The solution was allowed to warm to room temperature and was stirred for 2 hours. The solution was re-cooled to 0 ° C and tert-butyl chloride (2.78 g, 30 mmol) was added, stirring was continued for another 16 hours at room temperature. The reaction mixture was quenched with water and the aqueous phase was extracted with dichloromethane (2 × 50 ml). The organic phase was dried over sodium sulfate and evaporated in vacuo to give the title compound.

17.4 1,2-bis (1-adamantyl-tert-butylphosphinomethyl) ferrocene-bismethanesulfonate

The title compound was prepared following the procedure for Example 13 using 1-adamantyl-tert-butylphosphine (14.78 g, 0.066 mol) instead of diadamantylphosphine. Yield 9.80 g.

Example 18

Preparation of 1,2-bis (di-1-diamantylphosphinomethyl) ferrocene bismethanesulfonate

18.1 Diamantan

This compound was synthesized according to the method of Tamara et al. Organic Syntheses, CV 6, 378.

18.2 Di-1- (diamantane) chlorophosphinate

Received as di-1-adamantylchlorophosphinate in Example 14.1 using diamantane 20.0 g (0.106 mol) and AlCl ₃ (16.0 g, 0.12 mol). Yield 25.5 g, MM: 456.5, ³¹ P NMR: δ 87 ppm. (from).

18.3 Di-1- (diamantane) phosphine

Received as di-1-adamantylphosphine in Example 14.2 using 25.0 g of di-1- (diamantane) chlorophosphinate. Yield 14.0 g, MM: 406, ³¹ P NMR: δ 16.5 ppm. (from).

18.4 1,2-bis (di-1-diamantylphosphinomethyl) ferrocene bismethanesulfonate

The title compound was prepared following the procedure for Example 13 using di-1-diamantanphosphine (26.79 g, 0.066 mol) instead of diamantylphosphine. Yield 12.5 g.

Example 19

Preparation of 1,2-bis (di- (1,3,5,7-tetramethyl-6,9,10-trioxa-2-phosphaadamantylmethyl)) ferrocene

1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantane (obtained from Cytec, 14.0 g, 0.066 mol) was added to a solution of 1,2-bis (dimethylaminomethyl) ferrocene (example 1, 10 g, 0.033 mol) in anhydrous acetic acid (100 ml) under nitrogen atmosphere and the resulting mixture was stirred at 80 ° C for 72 hours. Anhydrous acetic acid was removed in vacuo at approximately 70 ° C, thereby obtaining the title crude product as an orange-yellow solid. It was washed with hot methanol to give the product as a mixture of isomers as an orange solid (12.0 g, 58%).

¹ H NMR (250 MHz; CDCl ₃ ): δ 4.25-3.95 (8H, broad, m), 3.46 (4H, broad), 1.57-2.0 (8H, broad. , m) 1.43-1.23 (24H, broad, m).

³¹ P NMR (101 MHz; CDCl ₃ ): δ -27.41 (br), -29.01 (s), -33.9 (br) ppm.

Elemental analysis: Found: C: 57.80%; H: 7.35%

Calculated: C: 57.87%; H: 7.40%

Example 20

Obtaining bismethyl iodide 1,2-bis (dimethylaminomethyl) ferrocene

Methyl iodide (23.28 g, 0.164 mol) was added to a solution of 1,2-bis (dimethylaminomethyl) ferrocene (Example 1, 20 g, 0.082 mol) in degassed methanol (100 ml), and the mixture was stirred at room temperature under nitrogen in within 24 hours. The resulting precipitate was filtered off, washed with ether and dried, yielding the title compound (43.0 g).

Elemental analysis: Found: C: 36.8%; H: 5.1%; N: 4.8%

Calculated: C: 37.0%; H: 5.2%; N: 4.8%

¹³ C NMR (D ₂ O): δ 53.27, 53.21, 53.15, 64.68, 71.77, 73.24, 74.13, 74.95.

Example 21

Obtaining 1,2-bis (dihydroxymethylphosphinomethyl) ferrocene

Potassium hydroxide (8.52 g, 0.152 mol) was added to a solution of tetrakis (hydroxymethyl) phosphonium chloride (Aldrich, 38.54 g of an 80% w / w aqueous solution, 0.162 mol) in degassed methanol (40 ml), and the mixture stirred at room temperature under nitrogen for 1 hour. The resulting mixture was added dropwise to a degassed solution of 1,2-bis (dimethylaminomethyl) ferrocene bismethyl iodide (Example 20, 19.98 g, 52.2 mmol) in methanol (40 ml) under nitrogen at room temperature with stirring. The resulting mixture was refluxed under nitrogen for 20 hours, the solvent was removed in vacuo to give a red precipitate. Water (30 ml), diethyl ether (85 ml) and triethylamine (35 ml) were added to the precipitate, and the solution was stirred at room temperature for 1 hour. The aqueous layer was separated and extracted with diethyl ether (2 × 30 ml). The combined ether extracts were washed with water (3 × 20 ml), dried over sodium sulfate and filtered. The ether was removed in vacuo to give the crude title compound (14.33 g, 94% yield) as a microcrystalline orange solid. The crude product was recrystallized from a warm dichloromethane / methanol solution with the addition of a light petroleum ether and cooled to give the title compound (10.69 g, 70% yield) as yellow-orange crystals.

Elemental analysis: Found: C: 48.44%; H: 4.12%; N: 0.0%

Calculated: C: 48.24%; H: 4.02%; N: 0.0%

¹ H NMR: δ 1.75 (s, broad), 2.70 (dd, 2H, J ² _HH 14.2 Hz, J ² _HP 6.6 Hz), 2.85 (dd, 2H, J ² _HV 14.2 Hz, J ² _HP 7.9 Hz), 3.71 (t, 1H, J _HH 2.44 Hz), 3.58 (s, 5H), 3.98 (d, 2H, J _HH 2.40 Hz), 4.06 (m, 8H).

¹ H { ³¹ P} NMR: δ 1.75 (s, broad), 2.70 (d, 14.3 Hz), 2.85 (d, 14.3 Hz), 4.04 (m, 1H ), 4.06 (s, 8H), 4.08 (s, 5H), 4.1 (m, 2H).

¹³ C NMR: δ 23.7 (d, J ¹ _MS 15.6 Hz), 63.0 (d, J ¹ _MS 15.6 Hz), 66.0 (s), 67.2 (d, J ³ _MS 9.2 Hz), 69.6 (s), 82.6 (d, J ² _MS 14.7 Hz).

³¹ P NMR: δ -14.7.

Infrared spectrum (CHCl ₃ / thin film, NaCl plates)

3337.8 (s, broad), additional peaks 1104, 2929.0, 3603.7, 3683.7 cm ^-1 .

Example 22

Obtaining 1,2-bis (diphosphinomethyl) ferrocene

1,2-bis (dihydroxymethylphosphinomethyl) ferrocene (Example 21, 5.45 g, 13.70 mmol) and sodium metabisulfite (5.21 g, 27.4 mmol) were added to a two-phase solvent system consisting of distilled water (60 ml ) and light fraction of petroleum ether (60 ml). The mixture was refluxed for 3 hours in air. The resulting mixture was cooled with stirring and the aqueous layer was removed. The organic layer was washed with distilled water, and the organic solvent was removed in vacuo to give the title compound (2.66 g, 70% yield) as an orange crystalline solid.

Elemental analysis: Found: C: 51.65%; H: 5.75%

Calculated: C: 51.80%; H: 5.76%

¹ H NMR (250 MHz; CDCl ₃ ): δ 2.7-2.8 (m, 4H), 3.17 (m, 2H), 3.18 (m, 2H), 4.04 (t, 1H , 2.54 Hz), 4.09 (d, 5H, J _HP 0.4 Hz), 4.13 (d, 2H, 2.54 Hz).

³¹ P NMR (101 MHz; CDCl ₃ ): δ 130.0 (t, J _HP 193.0 Hz).

¹³ C NMR (60 MHz; CDCl ₃ ): δ 12.9, 65.6, 67.3, 69.4, 86.9

¹³ C DEPT NMR (CDCl ₃ ): δ 12.9 (CH ² ), 65.6 (CH), 67.3 (CH), 69.40 (5HCH).

Fourier transform IR (chloroform, NaCl plates): 2298.5 cm ^-1 (strong).

Mass spectrum: Found m / z: 278.0088; Calculated m / z: 278.0077.

Example 23

Preparation of 1,2-bis-α, α- (P- (2,2,6,6-tetramethylphosphinan-4-one)) dimethylferrocene

2,6-dimethyl-2,5-heptadien-4-one (14.6 g, 0.106 mol) was added to 1,2-bis (diphosphinomethyl) ferrocene (Example 22, 14.7 g, 0.053 mol) and the mixture was heated up to 120 ° C in an atmosphere of nitrogen for 20 hours. The reaction mixture was cooled, the crude title compound was filtered off, washed with pentene (20 ml) and dried in vacuo to give the title compound as a yellow-orange solid (24.9 g, 85% yield). The title compound was characterized by ³¹ P NMR and mass spectrum data.

¹ H NMR (250 MHz; CDCl ₃ ): δ 4.32 (1H, broad), 4.08 (5H, broad), 4.02 (1H, broad), 3.94 (1H, broad. ), 2.84 (4H, broad), 1.8-2.5 (8H, broad), 1.05-1.4 (24H, broad).

³¹ P NMR (101 MHz; CDCl ₃ ): δ 4.15 ppm.

Elemental analysis: Found: C: 64.26%; H: 7.88%

Calculated: C: 65.03%; H: 7.94%

Example 24

Obtaining methylpropanoate from ethylene, carbon monoxide and methanol, catalyzed by the compound of the present invention

Autoclave equipped with mechanical stirring (Hastelloy) 2 liter capacity was evacuated and then charged with a solution of tri (dibenzylideneacetone) dipalladium (1,44 × CH10 ^-5 mol) and 1,2-bis (di-tert-butilfosfinometil) ferrocene from Example 2 (7 61 × 10 ^-5 mol) and methanesulfonic acid (2.25 × 10 ^-3 mol) in 300 ml of a mixture of methylpropanoate / methanol (70 wt.% Methylpropanoate). The autoclave was heated to 100 ° C, at this temperature ethylene (8 × 10 ⁵ Pa) was added over the partial pressure of the solvents, and an equimolecular mixture of carbon monoxide and ethylene (2 × 10 ⁵ Pa) was immediately added to the system using a pressure-controlled valve 10 × 10 ⁵ Pa, above the vapor pressure of the solvent. In a suitable case, the molar ratio of ethylene to carbon monoxide in the reactor was approximately 9: 1. The temperature of the reactor was maintained at 100 ° C, and during the course of the reaction, additional amounts of carbon monoxide and ethylene (in equimolar ratio) were added through a Tescom pressure control valve. No catalyst precipitation was observed.

For the catalyst, the initial reaction rates, measured in moles of methylpropanoate (MeP) per mole of palladium per hour, and the total value for the period measured in moles of methylpropanoate per mole of palladium were determined. The determination can be made by analyzing the amount of gas absorbed per unit time (speed) and the total amount of gas absorbed during the reaction, assuming the law of ideal gases and 100% methylpropanoate selectivity.

The reaction was repeated (experiment 2), and the initial reaction rates and the total value per cycle were calculated as described above. The data for both experiments are shown in table 1.

Table 1 Maximum (mol MeR / mol Pd / hour) of the initial velocity Total (mol MeP / mol Pd / hour) value for a period equal to 3 hours Experience 1 31,810 59,941 Experience 2 30,322 63,941

Reference Example 25

Obtaining methylpropanoate from ethylene, carbon monoxide and methanol, catalyzed by a known catalyst

Example 24 was repeated twice (experiments 3 and 4, respectively), except that the catalytic system was the same as described in WO 96/19434 and was obtained by loading into the autoclave three (dibenzylideneacetone) dipalladium (1.44 × 10 ^-5 mol), 1,2-bis (di-tert-butylphosphinomethyl) benzene (7.61 × 10 ^-5 mol) and methanesulfonic acid (2.25 × 10 ^-3 mol) in a mixture of methylpropanoate / methanol (300 ml, 70 wt.% Methylpropanoate).

The initial reaction rates (mol MeP / mol Pd per hour) and total values (mol Pd / mol MeP) for the catalyst were calculated as described above in Example 24. The results are presented below in table 2.

table 2 Maximum initial velocity (mol Pd / mol MeP / h) The total value for the period equal to 3 hours (mol Pd / mol MeR) Experience 3 29,730 48,386 Experience 4 30,335 51,997

The results demonstrate (see table 1 and table 2) that the catalyst of the present invention palladium 1,2-bis (di-tert-butylphosphinomethyl) ferrocene and the known catalyst palladium 1,2-bis (di-tert-butylphosphinomethyl) benzene show comparable initial catalytic reaction rates. However, the total values for the catalyst of the present invention are significantly higher than for the known catalyst of palladium 1,2-bis (di-tert-butylphosphinomethyl) benzene, thus showing that the compound of the present invention increases the carbonylation reaction rate compared to the known bidentate system.

Example 26

Obtaining methylpropanoate from ethylene, carbon monoxide and methanol, catalyzed by the compound of the present invention

Example 24 was repeated (experiments 5 to 9, respectively), except that the catalyst system used was obtained by loading 1,2-bis (di-1-adamantylphosphinomethyl) ferrocene-bismethanesulfonate into the autoclave (example 13 or 14, 7.61 × 10 ^-5 mol), three (dibenzylideneacetone) dipalladium (1.44 × 10 ^-5 mol) and methanesulfonic acid (2.25 × 10 ^-3 mol) in a mixture of methylpropanoate / methanol (300 ml, 70 wt.% Methylpropanoate) .

The initial reaction rates (mol MeP / mol Pd per hour) and total values (mol Pd / mol MeP) for the catalyst were calculated as described above in Example 24. The results are presented below in table 3.

Table 3 Maximum initial velocity (mol Pd / mol MeP / h) The total value for the period equal to 3 hours (mol Pd / mol MeR) Experience 5 52,854 67,885 Experience 6 37,034 64,996 Experience 7 35,986 64,441 Experience 8 40,781 62,108 Experience 9 39,251 62,108

The results demonstrate (see table 3 and table 2) that the catalyst of the present invention palladium 1,2-bis (di-1-adamantylphosphinomethyl) ferrocene-bismethanesulfonate shows a significantly higher initial catalytic reaction rate and a significantly higher total value for the period than the known palladium 1,2-bis (di-tert-butylphosphinomethyl) benzene catalyst, thus showing that the compound of the present invention increases the carbonylation reaction rate in comparison with the known bidentate system.

The results demonstrate (see table 3 and table 2) that the catalyst of the present invention palladium 1,2-bis (di-1-adamantylphosphinomethyl) ferrocene-bismethanesulfonate shows a significantly higher initial catalytic reaction rate and a significantly higher total value for the period than the known palladium 1,2-bis (di-tert-butylphosphinomethyl) benzene catalyst, thus showing that the compound of the present invention increases the carbonylation reaction rate in comparison with the known bidentate system.

Examples 27-32

1.0 Experiments with a standard load with a saturation of 70 wt.% MeP, 30 wt.% Meon

EXPERIMENT: Reaction solutions are prepared using standard Schlenk line technologies. In a nitrogen-purged glove box, 7.8 mg of Pd ₂ dba ₃ (1.45 · 10 ^-5 mol) and 6 equivalents of phosphine ligand (8.7 · 10 ^-5 mol) are weighed into a 500 ml round bottom flask. Then the flask is transferred to the Schlenk line. Then the ligand and palladium are dissolved in 125 ml of degassed methylpropionate. To facilitate complexation, palladium and ligand are first dissolved in methylpropionate and stirred for a period of 45 minutes before additional solvents are added to the solution. This makes possible the in situ formation of a neutral, trigonal planar complex Pd (0) [Pd (ligand) (dba)].

After complexation, 175 ml of a mixture of methylpropionate / methanol (50 wt.% Methanol, 50 wt.% Methylpropionate) are degassed and added to the flask. The addition of 420 μl of methanesulfonic acid (MSA) completes the preparation of the catalyst solution.

The catalytic solution is added to a pre-evacuated autoclave and heated to 100 ° C. Then the pressure in the autoclave is increased by 8 bar ethene relative to vapor pressure to obtain a total pressure of 10.2 bar at 100 ° C. Then the pressure in the autoclave is increased to 12.2 bar by adding a mixture of CO: ethene (1: 1, gaseous), supplied from a 10-liter tank. The control valve maintains the pressure in the autoclave during the reaction at 12.2 bar by continuously injecting gas from a 10-liter tank. The pressure of the tank, as well as the temperature of the reactor, is recorded over a period of 1 hour. The number of moles of substances produced at each moment of the reaction can be calculated from the pressure drop in the tank, assuming ideal gas behavior and 100% selectivity with respect to methyl propionate, which allows one to find the TON (number of revolutions) of the reaction.

Example 27

Maximum starting speed Speed in 1 hour TON after 1 hour 52039 39699 46093

From the above data, it can be seen that rutenocene gives active and stable catalysts.

2.0 Data obtained in pure methanol

The following data were obtained using the Pd: ligand: acid ratios of 1: 5: 20, using Pd (OAc) 2 as a source of palladium and methanol alone as a solvent. The following ligands were examined:

1.2-bis (di-tert-butylphosphinomethyl) benzene (comparative)

3. 1,2-bis (di-1-adamantylphosphinomethyl) ferrocene (Example 28)

4. 1,2-bis (di-1-congressylphosphinomethyl) ferrocene (Example 29)

5. 1,2-bis (di (3,5, dimethyl) -1-adamantylphosphinomethyl) ferrocene (Example 30)

6. 1,2-bis (di-phospha-adamantyl-phosphinomethyl) ferrocene (Example 31)

7. 1,2-bis (di-phoron-phosphinomethyl) ferrocene (Example 32)

EXPERIMENT: To carry out the data of these experiments, a 19F Hastella alloy autoclave is used in the semi-technical module 2. The autoclave is tested under pressure with nitrogen overnight. Standard reactions are as follows:

Pd (OAc) 2 (22 mg, 0.1 mmol) and the corresponding phosphine ligand (0.5 mmol) are weighed in an inert atmosphere glove box in a 500 ml 3-necked round-bottom flask. Upon removal, add 300 ml of degassed MeOH and the mixture is stirred for 1 hour. Methanesulfonic acid (140 μl, 2 mmol) was added to this solution and the weight of the catalyst solution was recorded. The autoclave is loaded with a solution and heated to 100 ° C. with stirring (vapor pressure 3.0 bar g) at 1000 rpm. The reaction is started by introducing a gaseous CO / ethylene mixture (1: 1) into the autoclave at a total pressure of 13.0 bar (g). The total pressure of the autoclave is controlled using TESCOM (13.0 bar g). This leads to a 1: 1 ratio of ethylene to CO at a total gas pressure of 10 bar (g) higher than the vapor pressure of the solvent. The temperature and pressure are maintained for 3 hours, during this period their values are recorded. After 3 hours, the gases are removed and the installation is cooled to room temperature. After lowering the pressure, the installation is emptied and the final mass of the solution is determined.

results

The results are presented in tabular form, with the increase in the mass of the reaction mixture used to calculate the TON of the catalyst. This is done by calculating the amount of MeR moles obtained in each reaction based on the increase in mass and dividing it by the number of moles of palladium (0.0001 moles in all cases). The TON of the catalyst calculated from gas consumption is slightly different from the TON in terms of weight gain, but the trends remain the same.

1,2-bis (di-tert-butylphosphinomethyl) benzene (comparative)

The table below describes in detail the individual and average weight gain obtained for the saturated alpha ligand under these conditions. There was no evidence of decomposition of the catalysts in any of these experiments, with all solutions leaving the autoclave being pale green / yellow solutions. Velocity profiles and TON profiles are illustrated in table 4 below.

Table 4 Ligand Link Weight increase (g) The average increase in mass (g) TON / Pd Average TON / Pd for 3 hours one 010403f 244.47 43655 one 020403f 258.98 251.86 46173 44950 one 030403f 252.13 45023

1,2-Bis (di-adamantylphosphinomethyl) ferrocene (Example 28)

The table below describes in detail the individual and average weight gain obtained for the ligand of 1,2-bis (di-1-adamantylphosphinomethyl) ferrocene under these conditions. Velocity profiles and TON profiles are illustrated in table 5 below.

Table 5 Ligand Link Weight increase (g) The average increase in mass (g) TON / Pd Average TON / Pd for 3 hours 3 060303a 364.97 64994 3 180303a 340.18 347.30 60746 62018 3 190303a 345.15 61634 3 200303a 339.88 60692

1,2-Bis (di-congresylphosphinomethyl) ferrocene (Example 29)

The table below describes in detail the individual and average weight gain obtained for the ligand of 1,2-bis (di-congressylphosphinomethyl) ferrocene under these conditions. Velocity profiles and TON profiles are illustrated in table 6 below.

Table 6 Ligand Link Weight increase (g) The average increase in mass (g) TON / Pd Average TON / Pd for 3 hours four 040304a 369.07 50926 four 050304a 313.44 49441 four 080304a 327.36 340.69 51350 60837 four 100304a 352.89 53472

1,2-Bis (di (3,5, dimethyl) -1-adamantylphosphinomethyl) ferrocene (Example 30)

The table below describes in detail the individual and average weight gain obtained for the ligand of 1,2-bis (di (3,5, dimethyl) -1-adamantylphosphinomethyl) ferrocene under these conditions. Velocity profiles and TON profiles are illustrated in table 7 below.

Table 7 Ligand Link Weight increase (g) The average increase in mass (g) TON / Pd Average TON / Pd for 3 hours 5 150304b 325.73 325.73 58166 58166

1,2-Bis (di-phospha-adamantyl-phosphinomethyl) ferrocene (Example 31)

The table below describes in detail the individual and average weight gain obtained for the ligand of 1,2-bis (di (3,5, dimethyl) -1-adamantylphosphinomethyl) ferrocene under these conditions. Velocity profiles and TON profiles are illustrated in table 8 below.

Table 8 Ligand Link Weight increase (g) The average increase in mass (g) TON / Pd Average TON / Pd for 3 hours 6 140803b 261.28 271.55 46657 48490 6 210803b 281.81 50323

Use 1960 μl MeSO ₃ N

1,2-Bis (di-phoron-phosphinomethyl) ferrocene (Example 6)

The table below describes in detail the individual and average weight gain obtained for the ligand of 1,2-bis (di (3,5, dimethyl) -1-adamantylphosphinomethyl) ferrocene under these conditions. Speed profiles and TON profiles are illustrated in table 9 below.

Table 9 Ligand Link Weight increase (g) The average increase in mass (g) TON / Pd Average TON / Pd for 3 hours 7 050903b 271.38 271.38 48460 48460

Use 1960 μl MeSO ₃ N

This dataset shows that the substituents on the phosphorus atom can vary, and all the examples given give an improvement over the comparative xylyl ligand.

Claims (45)

1. The compound obtained by the union: (a) a metal of group VIIIB or a compound thereof; and (b) a compound of formula I or a salt thereof:

where A ₁ and A ₂ , as well as A ₃ , A ₄ and A ₅ (when present), each independently, are lower alkylene; K is selected from the group consisting of hydrogen or —A ₃ —Q ³ (X ⁵ ) X ⁶ ; D is selected from the group consisting of hydrogen or —A ₄ —Q ⁴ (X ⁷ ) X ⁸ ; E is selected from the group consisting of hydrogen or —A ₅ —Q ⁵ (X ⁹ ) X ¹⁰ ; X ¹ represents CR ¹ (R ² ) (R ³ ), congressyl or adamantyl, X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), congressyl or adamantyl, or X ¹ and X ² together with Q ² , to which they are attached form an optionally substituted 2-phospha-adamantyl group, or X ¹ and X ² together with Q ² to which they are attached form a cyclic system of formula 1a; X ³ is CR ⁷ (R ⁸ ) (R ⁹ ), congressyl or adamantyl, X ⁴ is CR ¹⁰ (R ¹¹ ) (R ¹² ), congressyl or adamantyl, or X ³ and X ⁴ together with Q ¹ , to which they are attached form an optionally substituted 2-phospha-adamantyl group, or X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of formula 1b; X ⁵ is CR ¹³ (R ¹⁴ ) (R ¹⁵ ), congressyl or adamantyl, X ⁶ is CR ¹⁶ (R ¹⁷ ) (R ¹⁸ ), congressyl or adamantyl, or X ⁵ and X ⁶ together with Q ³ , to which they are attached form an optionally substituted 2-phosphaadamantyl group, or X ⁵ and X ⁶ together with Q ³ to which they are attached form a cyclic system of formula 1c; X ⁷ represents CR ¹³ (R ³² ) (R ³³ ), congressyl or adamantyl, X ⁸ represents CR ³⁴ (R ³⁵ ) (R ³⁶ ), congressil or adamantyl, or X ⁷ and X ⁸ together with Q ⁴ , to which they are attached form an optionally substituted 2-phospha-adamantyl group, or X ⁷ and X ⁸ together with Q ⁴ to which they are attached form a cyclic system of formula 1d; X ⁹ is CR ³⁷ (R ³⁸ ) (R ³⁹ ), congressyl or adamantyl, X ¹⁰ is CR ⁴⁰ (R ⁴¹ ) (R ⁴² ), congressyl or adamantyl, or X ⁹ and X ¹⁰ together with Q ⁵ , to which they are attached form an optionally substituted 2-phosphaadamantyl group, or X ⁹ and X ¹⁰ together with Q ⁵ to which they are attached form a cyclic system of formula 1e; Q ¹ and Q ² , as well as Q ³ , Q ⁴ and Q ⁵ (when present), each independently, are phosphorus; M represents a metal of group VIIIB or a cation thereof; L ₁ represents an optionally substituted cyclopentadienyl group; groups R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, each independently, are hydrogen or unsubstituted C ₁ -C ₆ alkyl; or one or more groups from R ¹ to R ³ , from R ⁴ to R ⁶ , from R ⁷ to R ⁹ , from R ¹⁰ to R ¹² , from R ¹³ to R ¹⁵ , from R ¹⁶ to R ¹⁸ , from R ³¹ to R ³³ , from R ³⁴ to R ³⁶ , from R ³⁷ to R ³⁹ , from R ⁴⁰ to R ⁴² , together with the carbon atom to which they are attached, each independently form a cyclic alkyl structure; or one or more groups of R ¹ and R ² , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ¹⁰ and R ¹¹ , R ¹³ and R ¹⁴ , R ¹⁶ and R ¹⁷ , R ³¹ and R ³² , R ³⁴ and R ³⁵ , R ³⁷ and R ³⁸ , R ⁴⁰ and R ⁴¹ , together with the carbon atom to which they are attached, each independently form a cyclic alkyl structure; cyclic systems of formulas 1a, 1b, 1c, 1d and 1e are represented by formulas

where R ⁴⁹ and R ⁵⁴ each independently represent hydrogen or unsubstituted C ₁ -C ₆ alkyl; groups from R ⁵⁰ to R ⁵³ , each independently, are optionally substituted C ₁ -C ₆ alkyl, trifluoromethyl or phenyl optionally substituted with unsubstituted C ₁ -C ₆ alkyl or OR ¹⁹ in which R ¹⁹ is an unsubstituted C ₁ -C ₆ alkyl; and each of Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ represents oxygen; and n = 1. 2. The compound according to claim 1 or 2, in which if K represents -A ₃ - (Q ³ (X ⁵ ) X ⁶ and E represents -A ₅ -Q ⁵ (X ⁹ ) X ¹⁰ , then D represents -A ₄ -Q ⁴ (X ⁷ ) X ⁸ . 3. The compound according to claim 1 or 2, in which the groups from R ⁵⁰ to R ⁵³ are the same or different and are unsubstituted C ₁ -C ₆ alkyl. 4. The compound according to claim 1 or 2, in which no group from R ¹ to R ¹⁸ and from R ³¹ to R ⁴² is hydrogen. 5. The compound according to claim 1 or 2, in which the adamantyl is an unsubstituted adamantyl or adamantyl substituted with one or more unsubstituted C ₁ -C ₈ alkyl substituents, or a combination thereof. 6. The compound according to claim 1 or 2, wherein 2-phospha-adamantyl is unsubstituted 2-phospha-adamantyl or 2-phospha-adamantyl substituted with one or more unsubstituted C ₁ -C ₈ alkyl substituents, or a combination thereof. 7. The compound according to claim 1 or 2, in which 2-phosphaadamantyl includes one or more oxygen atoms in the skeleton of 2-phosphaadamantyl. 8. The compound according to claim 1 or 2, in which congressil is an unsubstituted congressyl. 9. The compound according to claim 1 or 2, in which X 'is identical to X ³ and also X ⁵ , X ⁷ and X ⁹ when they are present. 10. The compound according to claim 1 or 2, in which X ² is identical to X ⁴ , as well as X ⁶ , X ⁸ and X ¹⁰ when they are present. 11. The compound according to claim 1 or 2, in which X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ) and X ⁴ represents CR ¹⁰ (R ¹¹ ) (R ¹² ). 12. The compound according to claim 1 or 2, in which X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents adamantyl, X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ) and X ⁴ is adamantyl. 13. The compound according to claim 1 or 2, in which X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents congressyl, X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ) and X ⁴ represents congressil. 14. The compound according to claim 1 or 2, in which the groups from X ¹ to X ⁴ each independently represent adamantyl. 15. The compound according to claim 1 or 2, in which the groups from X ¹ to X ⁴ each independently represent congressyl. 16. The compound according to claim 1 or 2, in which X ¹ and X ² together with Q ² to which they are attached form a cyclic system of the formula 1a, and X ³ and X ⁴ together with Q ¹ to which they are attached form cyclic system of formula 1b. 17. The compound according to claim 1 or 2, in which X ¹ and X ² together with Q ² to which they are attached form a 2-phospha-adamantyl group, and X ³ and X ⁴ together with Q ¹ to which they are attached form 2-phosphaadamantyl group. 18. The compound according to claim 1 or 2, in which K represents hydrogen. 19. The compound according to claim 1 or 2, in which K represents-A ₃ -Q ³ (X ⁵ ) X ⁶ . 20. The compound according to claim 19, in which -A ₃ -O ³ (X ⁵ ) X ⁶ is identical to -A ₂ -Q ¹ (X ³ ) X ⁴ . 21. The compound according to claim 1 or 2, in which D and E, together with the carbon atoms of the cyclopentadienyl ring to which they are attached, form an unsubstituted phenyl ring. 22. The compound according to claim 1 or 2, in which D and E are both hydrogen. 23. The compound according to claim 1 or 2, in which D represents -A ₄ -Q ⁴ (X ⁷ ) X ⁸ . 24. The compound according to item 23, in which -A ₄ -Q ⁴ (X ⁷ ) X ⁸ is identical to -A ₂ -Q ¹ (X ³ ) X ⁴ . 25. The compound according to paragraph 24, in which E represents hydrogen. 26. The compound according to claim 1 or 2, in which E represents-A ₅ -Q ⁵ (X ⁹ ) X ¹⁰ . 27. The compound according to p. 26, in which -A ₅ -Q ⁵ (X ⁹ ) X ¹⁰ is identical to -A ₂ -Q ¹ (X ³ ) X ⁴ . 28. The compound according to claim 1 or 2, in which A ₁ and A ₂ , as well as A ₃ , A ₄ and A ₅ , when present, each independently, are —CH ₂ - or —C ₂ H ₄ -. 29. The compound according to claim 1 or 2, in which A ₁ and A ₂ , as well as A ₃ , A ₄ and A ₅ , when present, are identical. 30. The compound according to clause 29, in which A ₁ and A ₂ , as well as A ₃ , A ₄ and A ₅ , when present, are —CH ₂ -. 31. The compound according to claim 1 or 2, in which L ₁ represents unsubstituted cyclopentadienyl. 32. The compound according to claim 1 or 2, in which M represents iron or its cation. 33. The compound according to claim 1 or 2, obtained by combining: (a) palladium or its compounds; and (b) a compound of formula I, as defined in any of the preceding paragraphs. 34. A method for producing a compound as defined in any one of claims 1 to 33, which comprises combining (a) a Group VIIIB metal or a compound thereof; and (b) a compound of formula I, as defined in any one of claims 1 to 33. 35. The compound of formula I

in which A ₁ , A ₂ , K, D, E, M, L ₁ , Q ¹ , Q ² , X ¹ , X ² , X ³ , X ⁴ and n are defined as indicated in any one of claims 1 to 33. 36. The method of obtaining the compounds of formula I, as defined in clause 35, comprising the interaction of the compounds of formula II, in which A ₁ , A ₂ , K, D, E, M, L ₁ and n are defined as indicated for the compounds of formula I, and LG ₁ and LG ₂ are suitable leaving groups, with a compound of formula IIIa and IIIb,

in which X ¹ , X ² , Q ² , X ³ , X ⁴ and Q ^{1 are} defined as indicated in any one of claims 1 to 33. 37. The compound of formula II, as defined in paragraph 36. 38. A method of obtaining a compound of formula I, in which K, D, E, M, A ₂ , A ₁ , L ₁ , Q ¹ , Q ² and n are defined as indicated in any one of claims ^{1 to} 33, and X ¹ and X ² together with Q ² to which they are attached form a cyclic system of formula Ia as defined in claim 1, and X ³ and X ⁴ together with Q ¹ to which they are attached form a cyclic system of formula Ib defined as indicated in any one of claims 1 to 33, comprising the interaction of the compounds of formula XV

in which K, D, E, M, A ₂ , A ₁ , L ₁ , Q ¹ , Q ² and n are defined as indicated in any one of claims 1 to 33, with a compound of formula XVIa and XVIb

in which Y ¹ , Y ² , from R ⁴⁹ to R ^{55 are} defined as indicated for the compounds of formula I. 39. The compound of formula XV, as defined in paragraph 38. 40. A method for carbonylating an ethylenically unsaturated compound, comprising reacting an ethylenically unsaturated compound with carbon monoxide and a co-reagent selected from the group of nucleophilic components containing a mobile hydrogen atom or molecular hydrogen, in the presence of a compound as defined in any one of claims 1 to 33. 41. The method according to p, in which the co-agent includes a compound containing a hydroxyl group. 42. The method of claim 40 or 41, wherein the ethylene unsaturated compound comprises ethylene, 1,3-butadiene, oct-1-ene or vinyl acetate, preferably ethylene. 43. The method according to p. 40 or 41, which further comprises the step of including a source of anions. 44. A catalytic composition comprising a compound according to any one of claims 1 to 33, attached to a carrier. 45. The use of a compound according to any one of claims 1 to 33 or a composition according to claim 44 as a catalyst for catalysis of the carbonylation reaction of ethylene unsaturated compounds.