Oxidative Addition of Disulfides to the Complex W(CO)3(phen)(EtCN). Synthesis, Structure, and Reactivity of W(CO)2(phen)(SR)2 (R = Ph, Me, CH2Ph, tBu; phen = 1,10-Phenanthroline) Coordinatively Unsaturated Complexes of Tungsten(II) That Reversibly Bind CO and Other Ligands

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

Research output: Contribution to journalArticle

33 Scopus citations

Abstract

The complex W(CO)3(phen)(EtCN) undergoes oxidative addition with disulfides forming the formally 16-electron complexes W(CO)2(phen)(SR)2 (R = Ph, tBu, Me, benzyl). The reactions proceed through intermediates identified spectroscopically as the coordinated disulfide complexes. The rate of oxidative addition of coordinated disulfides is in the order tBuSSBut ≪ MeSSMe < PhCH2SSCH2Ph < PhSSPh. The complexes W(CO)2(phen)(SR)2 undergo ligand addition, ligand substitution, and thiol/thiolate exchange reactions. Variable-temperature equilibrium studies yielded thermodynamic parameters for binding of CO to W(CO)2(phen)(SR)2: R = Ph, ΔH = -7.2 ± 0.5 kcal/mol, ΔS = -29 ± 3.5 cal/(mol deg); R = tBu, ΔH = -9.5 ± 0.5 kcal/mol, ΔS = -41 ± 3.5 cal/(mol deg). Reaction with trimethylphosphine yields an equilibrium mixture of the 18-electron adduct W(CO)2(phen)(PMe3)(SPh)2 as well as the 16-electron monocarbonyl complex W(CO)(phen)(PMe3)(SPh)2. Addition of trimethyl phosphite yields only W(CO)(phen)(P(OMe)3)(SPh)2. Pyridine, propionitrile, hydrogen, and THFdo not bind to the W(II) complexes. Reaction of W(CO)2(phen)(StBu)2 with 1 equiv of thiophenol yields W(CO)2(phen)(StBu)(SPh), which reacts with additional thiophenol to yield W(CO)2(phen)(SPh)2. Reaction with excess hydrogen sulfide yields W(CO)2(phen)(SH)2, which reacts further with thiophenol to yield W(CO)2(phen)(SPh)2. Crystal structures are reported for W(CO)2(phen)(SPh)2 and W(CO)(phen)(P(OMe)3)(SPh)2.

Original languageEnglish (US)
Pages (from-to)3899-3907
Number of pages9
JournalInorganic Chemistry
Volume33
Issue number18
DOIs
StatePublished - Aug 1 1994

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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