New anionic and dianionic polydentate systems featuring ancillary phosphinosulfides as ligands in coordination chemistry and catalysis

摘要

This article provides an overview of the chemistry of monoanionic S-P-S and dianionic S-C-S ligands featuring two phos-phinosulfide ligands as pendant groups.These new pincer-type structures are easily assembled from phosphinines and the bis-sulfide derivative of the bis(diphenylphosphino)methane,respectively.Monoanionic S-P-S pincer ligands easily coordinate group 10 and group 9 metal fragments through displacement reactions.Palladium(II) complexes of S-P-S ligands efficiently catalyze cross-coupling processes,allowing the formation of boronic esters and biphenyl derivatives.Rh(I) complexes of S-P-S ligands react in a regioselective way with small molecules (O_2,SO_2,CS_2,MeI) to afford the corresponding Rh(I) or Rh(HI) derivatives.S-C-S dianonic ligands,which are readily obtained through a bis-metallation at the central carbon atom of Ph_2P(=S)CH_2P(=S)Ph_2,react with Pd(II) and Ru(II) precursors to afford new carbene complexes.Samarium and thulium alky-lidene complexes of these S-C-S dianionic ligands were synthesized in a similar way.Reaction of the lanthanide derivatives with ketones or aldehydes yields olefinic derivatives through a 'Wittig-like' process.