Phospha-adamantane(s) catalytic system

1. A catalyst system capable of catalysing the carbonylation of an olefinally unsaturated compound, which catalyst system is obtainable by combining:

(a) a metal of Group VIB or Group VIIIB or a compound thereof: and

(b) a bidentate phosphine of general formula (I)

(Ad) s (CR 4 R 5 R 6 ) T Q 2 -A-(K,D)Ar(E,Z)-B-Q 1 (Ad) u (CR 1 R 2 R 3 ) v   (1)

wherein:

Ar is a bridging group comprising an optionally substituted aryl moiety to which the phosphorus atoms are linked on available adjacent carbon atoms;

A and B each independently represent lower alkylene;

K, D, E and Z are substituents of the aryl moiety (Ar) and each independently represent hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, OR 10 , OC(O)R 11 , C(O)R 12 , C(O)OR 13 , NR 14 R 15 , C(O)NR 16 R 17 , C(S)R 16 R 17 , SR 18 , C(O)SR 18 , or -J-Q 3 (Ad) w (CR 7 (R 8 )(R 9 )) x where J represents lower alkylene; or two adjacent groups selected from K, Z, D and E together with the carbon atoms of the aryl ring to which they are attached form a further phenyl ring, which is optionally substituted by one or more substituents selected from hydrogen, lower alkyl, halo, cyano, nitro, OR 10 , OC(O)R 11 , C(O)R 12 , C(O)OR 13 , NR 14 R 15 , C(O)NR 16 R 17 , C(S)R 16 R 17 , SR 18 or C(O)SR 18 ;

R 1 to R 6 each independently represent lower alkyl, aryl, or Het;

Ad each independently represent an optionally substituted adamantyl radical bonded to the phosphorous atom via any one of its tertiary carbon atoms, the said optional substitution being by one or more substituents selected from hydrogen, lower alkyl, halo, cyano, nitro, OR 10 , OC(O)R 11 , C(O)R 12 , C(O)OR 13 , NR 14 R 15 , C(O)NR 16 R 17 , C(S)R 16 R 17 , SR 18 or C(O)SR 18 ;

R 10 to R 18 each independently represent hydrogen, lower alkyl, aryl or Het;

S & U=0, 1 or 2 provided that S+U≧1;

T & V=0, 1 or 2 provided that T+V≦3;

W & X=0, 1 or 2;

Q 1 , Q 2 and Q 3 (when present) each independently represent phosphorous, arsenic or antimony and in the latter two cases references to phosphine or phosphorous above should be varied accordingly.

2. A catalyst system according to claim 1 wherein, the Group VIII B metal is palladium.

3. A catalyst system according to claim 1 , wherein R 1 to R 9 each independently represent lower alkyl, aralkyl or aryl.

4. A catalyst system according to claim 1 , wherein R 1 to R 9 each independently represent C 1 to C 6 alkyl, C 1 -C 6 alkyl phenyl (wherein the phenyl group is optionally substituted as defined herein) or phenyl (wherein the phenyl group is optionally substituted as defined herein).

5. A catalyst system according to claim 1 , wherein each Q 1 , Q 2 and Q 3 (when present) are the same.

6. A catalyst system according claim 1 , each Q 1 , Q 2 and Q 3 (when present) represents phosphorous.

7. A catalyst system according to claim 1 , wherein A, B and J (when present) each independently represent C 1 to C 6 alkylene which is optionally substituted as defined herein, for example with lower alkyl groups.

8. A catalyst system according to claim 1 , wherein when K, D, E or Z does not represent -J-Q 3 (Ad) w (CR 7 (R 8 )(R 9 )) x , K, D, E or Z represents hydrogen, lower alkyl, phenyl or lower alkylphenyl.

9. A catalyst system according to claim 1 , wherein when K, D, E and Z together with the carbon atoms of the aryl ring to which they are attached do not form a phenyl ring, K, D, E and Z each independently represent hydrogen, lower alkyl, phenyl or lower alkylphenyl.

10. A catalyst system according to claim 1 , wherein when two of K, D, E and Z together with the carbon atoms of the aryl ring to which they are attached form a phenyl ring, then the phenyl ring is optionally substituted with one or more substituents selected from aryl, lower alkyl (which alkyl group may itself be optionally substituted or terminated as defined below), Het, halo, cyano, nitro, OR 10 , OC(O)R 11 , C(O)R 12 , C(O)OR 13 , NR 14 R 15 , C(O)NR 16 R 17 , SR 18 , C(O)SR 18 or C(S)NR 16 R 17 wherein R 10 to R 18 each independently represent hydrogen or lower alkyl (which alkyl group may itself be optionally substituted or terminated as defined herein).

11. A catalyst system according to claim 1 , wherein S≧1 and u≧1.

12. A process for the carbonylation of an ethylenically unsaturated compound comprising contacting an ethylenically unsaturated compound with carbon monoxide and either water or an organic molecule having a hydroxyl functional group in the presence of a catalyst system in accordance with claim 1 .

13. A process according to claim 12 , wherein the organic molecule having a hydroxyl functional group may be branched or linear, and comprises an alkanol, particularly a C 1 -C 30 alkanol, including aryl alkanols, which may be optionally substituted with one or more substituents selected from lower alkyl, aryl, Het, halo, cyano, nitro, OR 10 , OC(O)R 11 , C(O)R 12 , C(O)OR 13 , NR 14 R 15 , C(O)NR 16 R 17 , C(S)R 16 R 17 , SR 18 or C(O)SR 18 as defined herein.

14. A process according to claim 12 , wherein the carbonylation of an ethylenically unsaturated compound is performed in one or more aprotic solvents.

15. A process according to claim 12 , wherein the reaction is carried out in the absence of any external added aprotic solvent ie. an aprotic solvent not generated by the reaction itself.

16. A process according to claim 12 , wherein the anion may be derived from or introduced as one or more of an acid having a pKa measured in aqueous solution at 18° C., of less than 4.

17. A process according to claim 12 , wherein ethylenically unsaturated compound contains 2 to 30 carbon atoms.

18. A catalyst system according to claim 1 , wherein the catalyst system includes in a liquid reaction medium a polymeric dispersant dissolved in a liquid carrier, said polymeric dispersant being capable of stabilising a colloidal suspension of particles of the group VI or VIIIB metal or metal compound of the catalyst system within the liquid carrier.

19. A catalyst system according to claim 1 , wherein each of the groups Rto R 3 , R 4 to R 6 and R 7 to R 9 together independently may form cyclic structures such as 1-norbornyl or 1-norbornadienyl.