Oxidative addition of thiols, and thiol/thiolate exchange reactions of low valent molybdenum and tungsten complexes. Synthetic, structural and calorimetric study of trigonal prismatic W(CO)2(1,10-phenanthroline)(3,4-toluenedithiolate)

Russell F. Lang, Telvin D. Ju, Jeffrey C. Bryan, Gregory J. Kubas, Carl D. Hoff

Research output: Contribution to journalArticle

7 Scopus citations

Abstract

Reactions of W(CO)3(phen)(EtCN) with butane thiols, thiophenol, 1,2-benzenedithiol, and 3,4-toluenedithiol have been investigated. Reaction of butanethiol results in simple ligand exchange to form the thiol complex W(CO)3(phen)(nortBuSH). Reaction with thiophenol results in oxidative addition to form the W(II) thiolate hydride complex W (CO)3(phen)(SPh)(H). The lower reducing power of Mo compared to W is demonstrated in that simple ligand binding of PhSH to Mo(0) occurs forming Mo(CO)3(phen)(PhSH). Reactions of arene dithiols with W(CO)3(phen)(EtCN) were found to proceed with initial oxidative addition of one S-H bond of the chelating dithiols to form W(CO)3(phen)(H)[S-arene(SH)]. These complexes slowly eliminate H2 and CO to form W(CO)2(phen)(arenedithiolate) complexes. The same complexes can be formed by thiol/thiolate exchange reactions: W(CO)2(phen)(SR)2 (R=tBu, Ph) react quantitatively with arene dithiol to yield W(CO)2(phen)(arenedithiolate). The crystal structure of W(CO)2(phen)(3,4-toluenedithiolate) has been determined and is trigonal prismatic rather than octahedral. Values for ΔH° (thiol/thiolate exchange) have been measured by solution calorimetry relative to W(CO)2(phen)(StBu)2=0.0 kcal mol-1; (CO)2(phen)(SPh)2=-7.2±0.4 kcal mol-1 and W(CO)2(phen)(3,4-toluenedithiolate)=-12.5±0.6 kcal mol-1.

Original languageEnglish (US)
Pages (from-to)157-164
Number of pages8
JournalInorganica Chimica Acta
Volume348
DOIs
StatePublished - May 15 2003

Keywords

  • Molybdenum complexes
  • Oxidative addition
  • Tungsten complexes

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Fingerprint Dive into the research topics of 'Oxidative addition of thiols, and thiol/thiolate exchange reactions of low valent molybdenum and tungsten complexes. Synthetic, structural and calorimetric study of trigonal prismatic W(CO)<sub>2</sub>(1,10-phenanthroline)(3,4-toluenedithiolate)'. Together they form a unique fingerprint.

  • Cite this