Substituted metal carbonyls. Part 21. [M(CO) 5 (dppf-P)][M = Cr, Mo or W; dppf = Fe(C 5 H 4 PPh 2 ) 2 ] as a metalloligand in heteropolymetallic aggregates of Au I , Pd II and Pt II . Crystal and molecular structures of [PtCl 2 {(µ-dppf)W(CO) 5 } 2 ] and [Mo(CO) 5 (dppf-P)]
Authors:
- Lai-Tee PhangLPLai-Tee Phang
- Steve C. F. Au-YeungSASteve C. F. Au-Yeung
- T. S. Andy HorTHT. S. Andy Hor
- Soo Beng KhooSKSoo Beng Khoo
- Zhong-Yuan ZhouZZZhong-Yuan Zhou
- Thomas C. W. MakTMThomas C. W. Mak
- 1 January 1993
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 1,p. 165-172
Abstract
The complexes [M(CO)5(dppf-P)][M = Cr, Mo or W; dppf = 1,1′-bis(diphenylphosphino)ferrocene] behave like a monodentate phosphine ligand and displace the labile ligands from [AuCl(SMe2)], trans-[PdCl2(PhCN)2] and cis-[PtCl2(dmso)2](dmso = dimethyl sulfoxide) to yield the corresponding dppf-bridged heteropolymetallic complexes of general formula [M′Clx{(µ-dppf)M(CO)5}y](M′= Au, x=y= 1; M′= Pd or Pt, x=y= 2). Only the trans isomers have been isolated for PdII and PtII. Isomerisation of the M′= Pt, M = Cr complex to the cis form, followed by partial elimination of [Cr2(CO)10(µ-dppf)] to form [PtCl2(dppf-P,P′)], after 3 d in CDCl3 was revealed by NMR spectroscopy. The solution characteristics of both geometrical isomers of the representative M′= Pt, M = Cr complex have been established by two-dimensional NMR studies. UV-Photolytic degradation of the M′= Pd or Pt, M complexes generally gave [M(CO)6], [M(CO)4(dppf-P,P′)], [M2(CO)10(µ-dppf)] and [M′Cl2(dppf)]. The molecular structures of trans-[PtCl2{(µ-dppf)W(CO)5}2] and [Mo(CO)5(dppf-P)] have been determined. The former represents a trimetallic pentanuclear aggregate and the latter a metalloligand with a pendant phosphine on a bimetallic complex. Cyclic voltammetry of all the complexes has been examined and generally reveals one chemically reversible phosphinoferrocene-based oxidation, followed by an irreversible oxidation of the complex.Keywords
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