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Synthesis, conformational analysis and catalytic properties of a chiral P, C-chelated rhodium(I) complex with a binapium ylide ligand

Novel preparative, structural and catalytic features of the rhodium complex [(η 2 -(R)-binapCH 2 )Rh(cod)] involving a P,C-chelated binapium ylide («ylipho»-like) ligand are presented. The trisphosphorus salt [(η 2 -(R)-binapCH 2 )Rh(cod)][PF 6 ] is described. The first evidence of a catalytic activity of ylide-containing transition metal complexes for hydrosilylation of ketones is disclosed. DFT calculation on a model complex indicate an extreme kinetic flexibilty of the chiral eight-membered rhodacycle at the level of the Rh-CP + bond, which could be naturally related to the rather low enantioselectivity (≤ 15%) of the hydrosilylation process.