Apparent Fluxionality in Diethyl(triethylphosphine)platinum(II), a Coordinatively Unsaturated Intermediate in β-Hydride Elimination

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

Research output: Contribution to journalArticle

Abstract

The thermal decomposition of (Et3P)2Pt(C2H5)2 proceeds by rate-limiting dissociation of triethylphosphine, followed by β-hydride elimination from a PtC2H5 group (Scheme I, 2 →• 3). Isotopic labeling and kinetics indicate that the two platinum-bound ethyl groups of the coordinatively unsaturated intermediate diethyl(triethylphosphine)platinum(II) lose hydrogen with approximately equal probability (Scheme I). Thus, either side-to-side motion of the triethylphosphine ligand within a "T"-shaped complex (2a ⇆ 2b, Scheme I) is fast relative to reductive elimination of ethane from 3 or some other process or geometry renders the ethyl groups roughly equivalent on this time scale.

Original languageEnglish (US)
Pages (from-to)1676-1678
Number of pages3
JournalJournal of the American Chemical Society
Volume103
Issue number7
DOIs
StatePublished - Apr 1981
Externally publishedYes

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Platinum
platinum
Hydrides
Ethane
thermal decomposition
ethane
Labeling
ligand
Hydrogen
Pyrolysis
Hot Temperature
Ligands
hydrogen
timescale
geometry
kinetics
Kinetics
Geometry
labelling
rate

ASJC Scopus subject areas

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

Cite this

Apparent Fluxionality in Diethyl(triethylphosphine)platinum(II), a Coordinatively Unsaturated Intermediate in β-Hydride Elimination. / McCarthy, Thomas J.; Nuzzo, Ralph G; Whitesides, George M.

In: Journal of the American Chemical Society, Vol. 103, No. 7, 04.1981, p. 1676-1678.

Research output: Contribution to journalArticle

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abstract = "The thermal decomposition of (Et3P)2Pt(C2H5)2 proceeds by rate-limiting dissociation of triethylphosphine, followed by β-hydride elimination from a PtC2H5 group (Scheme I, 2 →• 3). Isotopic labeling and kinetics indicate that the two platinum-bound ethyl groups of the coordinatively unsaturated intermediate diethyl(triethylphosphine)platinum(II) lose hydrogen with approximately equal probability (Scheme I). Thus, either side-to-side motion of the triethylphosphine ligand within a {"}T{"}-shaped complex (2a ⇆ 2b, Scheme I) is fast relative to reductive elimination of ethane from 3 or some other process or geometry renders the ethyl groups roughly equivalent on this time scale.",
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AB - The thermal decomposition of (Et3P)2Pt(C2H5)2 proceeds by rate-limiting dissociation of triethylphosphine, followed by β-hydride elimination from a PtC2H5 group (Scheme I, 2 →• 3). Isotopic labeling and kinetics indicate that the two platinum-bound ethyl groups of the coordinatively unsaturated intermediate diethyl(triethylphosphine)platinum(II) lose hydrogen with approximately equal probability (Scheme I). Thus, either side-to-side motion of the triethylphosphine ligand within a "T"-shaped complex (2a ⇆ 2b, Scheme I) is fast relative to reductive elimination of ethane from 3 or some other process or geometry renders the ethyl groups roughly equivalent on this time scale.

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