期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 15, 期 40, 页码 10504-10513出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200901178
关键词
carbonylation; diphosphanes; fluorinated phosphanes; palladium; reaction mechanisms
资金
- SASOL(UK)
- EPSRC
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(BH3)(tBu)(Ar)] with dihaloalkanes. Non-symmetric ligands were prepared from a new stable precursor, tBu(2)P(BH3)(CH2)(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 [PdCl2(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.
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