The synthesis, X-ray structure, and catalytic properties of the first cobalt carbonyl dimer supported by a N-heterocyclic carbene ligand Co(2)(CO)(6)(IMes)(2) [IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] is reported.

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The synthesis of four new bulky bidentate phosphines that possess both tert-butyl and trifluoromethylphenyl substituents is described. Symmetric ligands were readily obtained by alkylation of phosphidoboranes of the type Li[P(BH(3))(tBu)(Ar)] with dihaloalkanes. Non-symmetric ligands were prepared from a new stable precursor, tBu(2)P(BH(3))(CH(2))(3)Br, that should prove useful for other ligand syntheses. Palladium(II) complexes of the four new ligands were prepared and were characterised by spectroscopic methods, microanalysis and X-ray crystallography. The new [PdCl(2)(L)] complexes were evaluated as catalysts for the hydroxycarbonylation of styrene and found to give unprecedented regioselectivity and yields for a diphosphine-based catalyst. A study on promoter effects reveals that the presence of acid and chloride is necessary to achieve such selectivities. It has been proposed in the literature that such conditions result in a new pathway in which styrene is converted into 2-phenethyl chloride, with the latter being the real substrate in the reaction. However, a deuterium labelling study seems to rule out this mechanism, at least under the conditions used herein.