Unsymmetrical complexes containing the linear tetraphosphine ligand DPPEPM
摘要:
The tetraphosphine DPPEPM reacts with [PtMe2(cod)] to produce [PtMe2(DPPEPM-PP)] (1) in near quantitative yield. On standing in solution, the free P atoms become oxidized to give [PtMe2(DPPEPM(O)(2)-PP)] (1a), which has been characterized by X-ray crystallography. In contrast, reactions of DPPEPM with [MCl2(cod)] (M = Pd, Pt) yield ionic products of the form [M(DPPEPM-PP)2]MC]4 (3, 4). When a solution of the platinum complex was allowed to stand, crystals of [Pt(mu-Cl)(mu-DPPEPM)(2)]Cl-3 (5) were obtained. In a third set of reactions, treatment of [PtCIR(cod)] (R = Me, Ph) or [PdClMe(cod)] with DPPEPM gives species of the type [MR(DPPEPM-PPP)]Cl (6-8), in which one of the internal P atoms is uncoordinated. Reactions of [PtR2(DPPEPM-PP)] with [PtR2'(cod)] or [MCl2(Cod)] (M = Pd, Pt), or of [PtR(DPPEPM-PPP)]Cl with [MCl2(cod)], lead to unsymmetrical bimetallic complexes. [PtMe2(mu-DPPEPM)PdCl2] (11) and [PtClPh(mu-DPPEPM)PdCl2] (14) have been characterized crystallographically. Trimetallic complexes of the form [{PtR2(mu-DPPEPM)}(2)M][MCl4] (M = Pd, Pt, 15-17) are produced by reaction of [PtR2(DPPEPM-PP)] with [MCl2(cod)]. (c) 2005 Elsevier B.V. All rights reserved.
Approaches to bi- and trimetallic platinum and palladium complexes using the DPPEPM ligand
作者:Padma Nair、Gordon K. Anderson、Nigam P. Rath
DOI:10.1016/j.inoche.2003.08.004
日期:2003.10
Bis (diphenylphosphinoethyl)phenylphosphino}methane (DPPEPM) reacts with [PtR2(cod)] in 1:1 ratio to give [PtR2? (DPPEPM-PP)] (2a, R = Me; 2b, R = Ph), whereas with [PtCl2(cod)] or [PdCl2(cod)] it yields the ionic species [M(DPPEPM-PP)(2)](2+) (3 and 4). With [MClMe(cod)], the product is [MMe(DPPEPM-PPP)](+) (5, M Pt; 6, M = Pd), in which one of the internal P atoms of the ligand is uncoordinated. These complexes undergo oxidation of the free P atom to give 7 and 8 on standing in solution. Complexes 2-4 may be used to construct bimetallic and trimetallic mixed metal complexes. The molecular structures of 7 and [PtMe2(mu-DPPEPM)PdCl2] (11) are reported. (C) 2003 Elsevier B.V. All rights reserved.