Reactions of R2P–P(SiMe3)2 with [(R3′P)2PtCl2]. Syntheses and structures of [μ2-(1,2:2-η-P2){Pt(PEt3)2}2{Pt(PEt3)2Cl}]+Cl−, [{(Et2PhP)2Pt}2P2], [{(p-Tol3P)2Pt}2P2] and [(p-Tol3P)ClPt(μ-PPh2)2Pt(p-Tol3P)Cl]

The reactions of diphosphanes R2P–P(SiMe3)2 (R = Ph, tBu, Et2N and iPr2N) with [(R3′P)2PtCl2] (R3′P=Me3P, Et3P, Et2PhP, EtPh2P and p-Tol3P) are very complex. The main reaction pathway is splitting of the P–P bond of the parent R2P–P(SiMe3)2 followed by formation of [{(R3′P)2Pt}2P2], R2P–PR2 and other products which have been characterized by 31P NMR spectroscopy. The molecular structures of [{(Et2PhP)2Pt}2P2], [{(p-Tol3P)2Pt}2P2] · 2Et2O, [μ2-(1,2:2-η-P2){Pt(PEt3)2}2{Pt(PEt3)2Cl}]+Cl− and [(p-Tol3P)ClPt(μ-PPh2)2Pt(p-Tol3P)Cl] have been determined by single-crystal X-ray structural analysis.

Graphical abstractIn reactions of R2P–P(SiMe3)2 with [(R3′P)2PtCl2] cleavages of the P–P bond of the parent diphosphane have been observed. The main products are diphosphorus complexes of Pt(0).Figure optionsDownload full-size imageDownload as PowerPoint slide