A SF Derivative of Triphenylphosphine as an Electron-Poor Ligand Precursor for Rh and Ir Complexes.

The synthesis of the triarylphosphine, P(-CHSF) containing a SF group, has been achieved. The experimental and theoretical studies showed that P(-CHSF) is a weaker σ-donor when compared with other substituted triarylphosphines, which is consistent with the electron-withdrawing effect of the SF moiety. The studies also revealed a moderate air stability of the phosphine. The σ-donor capabilities of P(-CHSF) were estimated from the phosphorus-selenium coupling constant in SeP(-CHSF) and by DFT calculations. The behavior of P(-CHSF) as ligand has been investigated by the synthesis of the iridium and rhodium complexes [MCl(COD){P(-CHSF)}], [MCl(CO){P(-CHSF)}] (M = Ir, Rh), or [Rh(-Cl)(COE){P(-CHSF)}], and the molecular structures of [IrCl(COD){P(-CHSF)}] and [Rh(-Cl)(COE){P(-CHSF)}] were determined by single X-ray diffraction. The structures revealed a slightly larger cone angle for P(-CHSF) when compared to other -substituted triarylphosphines.