First- and second-order mechanisms for oxidative addition for bound methyl disulfide in the complex W(CO)3(phen) (MeSSMe)

Telvin D. Ju, Kenneth B. Capps, Gerald C. Roper, Russell F. Lang, Carl Hoff

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The rate of oxidative addition of methyl disulfide in the complex W(CO)3(1,10-phenanthroline)(MeSSMe) in methylene chloride has been studied. The dominant reaction pathway is second order in metal complex and inhibited by excess methyl disulfide. Formation of a dinuclear complex [W(CO)3(phen)]2(MeSSMe) is proposed to lead to the transition state for cleavage of the sulfur-sulfur bond in the second-order mechanism. In neat methyl disulfide, or in concentratred solutions of methyl disulfide at low metal complex concentrations, the reaction occurs at reduced rate and follows a first-order mechanism. Addition of Mo(CO)3(1,10-phenanthroline)(MeSSMe) to the corresponding tungsten complex results in a ten-fold increase in the rate of oxidative addition of the tungsten complex and production of Mo(CO)4(1,10-phenanthroline) as the sole molybdenum-containing product. The faster rate of reaction in the presence of the molybdenum complex is attributed to the faster formation of the heteronuclear dinuclear intermediate by initial loss of MeSSMe from the molybdenum versus tungsten center. Additional kinetic/mechanistic studies are described using a new flow-through FT-IR/microscope reaction system designed to allow convenient monitoring of small quantities of sensitive/hazardous reactants.

Original languageEnglish
Pages (from-to)488-498
Number of pages11
JournalInorganica Chimica Acta
Volume270
Issue number1-2
StatePublished - Apr 2 1998

Fingerprint

disulfides
Carbon Monoxide
Molybdenum
Tungsten
Metal complexes
molybdenum
tungsten
Coordination Complexes
Sulfur
sulfur
Dichloromethane
Methylene Chloride
Microscopes
methylene
metals
cleavage
Kinetics
Monitoring
chlorides
microscopes

Keywords

  • Carbonyl complexes
  • Disulfide complexes
  • Kinetics and mechanism
  • Oxidative addition
  • Tungsten complexes

ASJC Scopus subject areas

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

Cite this

First- and second-order mechanisms for oxidative addition for bound methyl disulfide in the complex W(CO)3(phen) (MeSSMe). / Ju, Telvin D.; Capps, Kenneth B.; Roper, Gerald C.; Lang, Russell F.; Hoff, Carl.

In: Inorganica Chimica Acta, Vol. 270, No. 1-2, 02.04.1998, p. 488-498.

Research output: Contribution to journalArticle

Ju, Telvin D. ; Capps, Kenneth B. ; Roper, Gerald C. ; Lang, Russell F. ; Hoff, Carl. / First- and second-order mechanisms for oxidative addition for bound methyl disulfide in the complex W(CO)3(phen) (MeSSMe). In: Inorganica Chimica Acta. 1998 ; Vol. 270, No. 1-2. pp. 488-498.
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N2 - The rate of oxidative addition of methyl disulfide in the complex W(CO)3(1,10-phenanthroline)(MeSSMe) in methylene chloride has been studied. The dominant reaction pathway is second order in metal complex and inhibited by excess methyl disulfide. Formation of a dinuclear complex [W(CO)3(phen)]2(MeSSMe) is proposed to lead to the transition state for cleavage of the sulfur-sulfur bond in the second-order mechanism. In neat methyl disulfide, or in concentratred solutions of methyl disulfide at low metal complex concentrations, the reaction occurs at reduced rate and follows a first-order mechanism. Addition of Mo(CO)3(1,10-phenanthroline)(MeSSMe) to the corresponding tungsten complex results in a ten-fold increase in the rate of oxidative addition of the tungsten complex and production of Mo(CO)4(1,10-phenanthroline) as the sole molybdenum-containing product. The faster rate of reaction in the presence of the molybdenum complex is attributed to the faster formation of the heteronuclear dinuclear intermediate by initial loss of MeSSMe from the molybdenum versus tungsten center. Additional kinetic/mechanistic studies are described using a new flow-through FT-IR/microscope reaction system designed to allow convenient monitoring of small quantities of sensitive/hazardous reactants.

AB - The rate of oxidative addition of methyl disulfide in the complex W(CO)3(1,10-phenanthroline)(MeSSMe) in methylene chloride has been studied. The dominant reaction pathway is second order in metal complex and inhibited by excess methyl disulfide. Formation of a dinuclear complex [W(CO)3(phen)]2(MeSSMe) is proposed to lead to the transition state for cleavage of the sulfur-sulfur bond in the second-order mechanism. In neat methyl disulfide, or in concentratred solutions of methyl disulfide at low metal complex concentrations, the reaction occurs at reduced rate and follows a first-order mechanism. Addition of Mo(CO)3(1,10-phenanthroline)(MeSSMe) to the corresponding tungsten complex results in a ten-fold increase in the rate of oxidative addition of the tungsten complex and production of Mo(CO)4(1,10-phenanthroline) as the sole molybdenum-containing product. The faster rate of reaction in the presence of the molybdenum complex is attributed to the faster formation of the heteronuclear dinuclear intermediate by initial loss of MeSSMe from the molybdenum versus tungsten center. Additional kinetic/mechanistic studies are described using a new flow-through FT-IR/microscope reaction system designed to allow convenient monitoring of small quantities of sensitive/hazardous reactants.

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