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Dipalladium and diplatinum bis(μ-alkanethiolato) complexes with a planar MS ring

Journal of the Chemical Society, Dalton Transactions, ISSN: 1472-7773, Issue: 19, Page: 2817-2826
1992
  • 76
    Citations
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  • 5
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Metric Options:   Counts1 Year3 Year

Metrics Details

  • Citations
    76
    • Citation Indexes
      76
  • Captures
    5

Article Description

Mononuclear complexes of formula [M(SR)(dppe)] (M = Pd 1 or Pt 2; R = CHNMe, dppe = PhPCHCHPPh) are formed in reactions of [MCl(dppe)] with the sodium salt of 4-mercapto-1-methylpiperidine NaSR in acetonitrile-methanol solution. Subsequent reaction of 1 with [PdCl(dppe)] and of 2 with [PtCl(dppe)] in acetonitrile solution produces the bridged dinuclear cationic complexes [M(μ-SR)(dppe)], which are obtained as crystalline salts with tetraphenylborate anions (M = Pd 3 or Pt 4). An apparently mixed PtPd product 5 is formed in an analogous reaction from 1 and [PtCl(dppe)] or from 2 and [PdCl(dppe)]. The structures of complexes 1-5 have been determined crystallographically. Complexes 1 and 2 are isostructural, with a slightly distorted square-planar cis-MPS co-ordination geometry. The isostructural complexes 3-5 also show square-planar co-ordination; the two aminothiolate ligands act as bridges between the metal atoms, giving a precisely planar central MS ring. In all five structures the MPC chelate rings have a twist conformation. The nitrogen atoms of the aminothiolates are not co-ordinated to the metal atoms. Infrared and H, P and Pt NMR spectra are presented and discussed. The combined evidence suggests that 5 is essentially a simple solid-solution mixture of pure complexes 3 and 4 in variable proportions, with at most a minor component of a genuinely heterobimetallic complex.

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