Synthesis of a novel volatile platinum complex for use in CVD and a study of the mechanism of its thermal decomposition in solution

Christopher D. Tagge, Robert D. Simpson, Robert G. Bergman, Michael J. Hosteller, Gregory S. Girolami, Ralph G. Nuzzo

Research output: Contribution to journalArticlepeer-review

Abstract

The synthesis, characterization, chemical vapor deposition, and mechanistic investigation of the thermal decomposition in aromatic solvents of cis-bis(η21-pent-4-en-1-yl)platinum (1) are described. Complex 1 has a unique chelated structure, giving rise to enhanced volatility, and has proved useful for the chemical vapor deposition of thin platinum films under mild conditions. Films deposited on a glass slide in a hot walled glass tube at 175°C have an elemental composition of 82% Pt and 18% C. Kinetic, deuterium labeling, and chemical trapping experiments indicate that the decomposition of 1 in aromatic solvents proceeds by reversible β-hydride elimination followed by reversible dissociation of 1,4-pentadiene to give a 3-coordinate platinum hydride intermediate (9). Reductive elimination of 1-pentene from 9 deposits metallic platinum. The rate of decomposition exhibits a significant β-deuterium isotope effect of k(H)/k(D) = 3.8 ± 0.3. Added olefins are rapidly isomerized during the decomposition of 1; trapping experiments with diphenylacetylene indicate that intermediate 9 is the highly active catalyst that is responsible for the alkene isomerization.

Original languageEnglish (US)
Pages (from-to)2634-2643
Number of pages10
JournalJournal of the American Chemical Society
Volume118
Issue number11
DOIs
StatePublished - Mar 20 1996

ASJC Scopus subject areas

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

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