P–C bond cleavage in dppm derivatives: X-ray structure of [Pd2(μ2-P,C-PPh2CHPOPh2)(μ2-dppm)Cl(PPh2Me)

Abstract

cis -[PdCl 2 (dppm)] [dppm = 1,2-bis(diphenylphosphino)methane] reacts with NaOH in ethanol to afford [Pd 2 (μ 2 - P , C -PPh 2 CHPOPh 2 )(μ 2 -dppm)Cl(PPh 2 Me)], which clearly shows different aspects of the formation of PPh 2 Me from the starting dppm ligand, especially the μ 2 - P , C methanide coordination. The Pd–Pd bond length of 2.6754(4) Å is in the usual range for dipalladium(I) compounds. cis -[PdCl 2 (dppm)] reacts with NaOH in ethanol to afford [Pd 2 (μ 2 - P , C -PPh 2 CHPOPh 2 )(μ 2 -dppm)Cl(PPh 2 Me)], which clearly shows different aspects of the formation of PPh 2 Me by P–C cleavage from the starting dppm ligand, especially the μ 2 - P , C methanide coordination. ► P–C bond cleavage of dppm complex with formation of PPh 2 Me complex. ► X‐ray structure of one of the few examples of μ 2 - P , C - coordination of a dppm-H derivative. ► Coexistence of both PPh 2 Me and μ 2 - P , C -PPh 2 CHPOPh 2 , showing that the former should precede the latter.