Mechanisms of Thermal Decomposition of Diethylbis( triethy lphosphine )platinum( II)

Thomas J. McCarthy, Ralph G Nuzzo, George M. Whitesides

Research output: Contribution to journalArticlepeer-review

Abstract

The mechanism of thermal decomposition of diethylbis(triethylphosphine)platinum(II) (L2PtEt2) to ethylenebis(triethylphosphine)platinum(0) and ethane in cyclohexane depends on the concentration [L] of triethylphosphine added to the solution When [L] ≃ 0 M, the overall rate-limiting step in the decomposition is dissociation of triethylphosphine from L2PtEt2; when [L] ≃ 0.3 M, the rate-limiting step is reductive elimination of ethane from an intermediate, ethylene(triethylphosphine)hydridoethylplatinum(II); when [L] ≥ 1.6 M, the most probable mechanism involves rate-limiting reductive elimination of ethane from ethylhydridobis(triethylphosphine)(ethylene)platinum(II). The deuterium kinetic isotope effect for reductive elimination of ethane from L(ethylene)Pt(H,D)Et is kH/kD ≃ 3.3 Activation parameters for each reaction indicate that entropy terms (especially of dissociation and reductive elimination of ligands from platinum) play an important role in determining which process is most rapid.

Original languageEnglish (US)
Pages (from-to)3396-3403
Number of pages8
JournalJournal of the American Chemical Society
Volume103
Issue number12
DOIs
StatePublished - Jun 1981
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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