Heats of reaction of HMo(CO)3(C5R5) (R = H, CH3) with diphenyldisulfide and of formation of the clusters [PhSMo(CO)x(C5H5)]2, x = 1,2. Thermodynamic study of molybdenum-sulfur bond strengths

Shakti L. Mukerjee, Alberto A. Gonzalez, Steven P. Nolan, Telvin D. Ju, Russell F. Lang, Carl Hoff

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Abstract

The enthalpies of reaction of HMo(CO)3C5R5 (R = H, CH3) with diphenyldisulfide producing PhSMo(CO)3C5R5 and PhSH have been measured in toluene and THF solution (R = H, ΔH= -8.5 ± 0.5 kcal mol-1 (tol), -10.8 ± 0.7 kcal mol-1 (THF); R = CH3, ΔH = -11.3±0.3 kcal mol-1 (tol), -13.2±0.7 kcal mol-1 (THF)). These data are used to estimate the MoSPh bond strength to be on the order of 38-41 kcal mol-1 for these complexes. The increased exothermicity of oxidative addition of disulfide in THF versus toluene is attributed to hydrogen bonding between thiophenol produced in the reaction and THF. This was confirmed by measurement of the heat of solution of thiophenol in toluene and THF. Differential scanning calorimetry as well as high temperature calorimetry have been performed on the dimerization and subsequent decarbonylation reactions of PhSMo(CO)3Cp yielding [PhSMo(CO)2Cp]2 and [PhSMo(CO)Cp]2. The enthalpies of reaction of PhSMo(CO)3Cp and [PhSMo(CO)2Cp]2 with PPh3, PPh2Me and P(OMe)3 have also been measured. The disproportionation reaction: 2[PhSMo(CO)2Cp]2 → 2PhSMo(CO)3Cp + [PhSMP(CO)Cp]2 is reported and its enthalpy has also been measured. These data allow determination of the enthalpy of formation of the metal-sulfur clusters [PhSMo(CO)nC5H5]2, n = 1,2.

Original languageEnglish
Pages (from-to)175-182
Number of pages8
JournalInorganica Chimica Acta
Volume240
Issue number1-2
DOIs
StatePublished - Jan 1 1995

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Molybdenum
Carbon Monoxide
Sulfur
molybdenum
Enthalpy
sulfur
Thermodynamics
Toluene
heat
thermodynamics
enthalpy
toluene
heat measurement
Dimerization
Calorimetry
heat of solution
disulfides
Differential scanning calorimetry
Hydrogen bonds
dimerization

Keywords

  • Carbonyl complexes
  • Enthalpy of reaction
  • Molybdenum complexes
  • Phenylsulfide complexes

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Heats of reaction of HMo(CO)3(C5R5) (R = H, CH3) with diphenyldisulfide and of formation of the clusters [PhSMo(CO)x(C5H5)]2, x = 1,2. Thermodynamic study of molybdenum-sulfur bond strengths. / Mukerjee, Shakti L.; Gonzalez, Alberto A.; Nolan, Steven P.; Ju, Telvin D.; Lang, Russell F.; Hoff, Carl.

In: Inorganica Chimica Acta, Vol. 240, No. 1-2, 01.01.1995, p. 175-182.

Research output: Contribution to journalArticle

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title = "Heats of reaction of HMo(CO)3(C5R5) (R = H, CH3) with diphenyldisulfide and of formation of the clusters [PhSMo(CO)x(C5H5)]2, x = 1,2. Thermodynamic study of molybdenum-sulfur bond strengths",
abstract = "The enthalpies of reaction of HMo(CO)3C5R5 (R = H, CH3) with diphenyldisulfide producing PhSMo(CO)3C5R5 and PhSH have been measured in toluene and THF solution (R = H, ΔH= -8.5 ± 0.5 kcal mol-1 (tol), -10.8 ± 0.7 kcal mol-1 (THF); R = CH3, ΔH = -11.3±0.3 kcal mol-1 (tol), -13.2±0.7 kcal mol-1 (THF)). These data are used to estimate the MoSPh bond strength to be on the order of 38-41 kcal mol-1 for these complexes. The increased exothermicity of oxidative addition of disulfide in THF versus toluene is attributed to hydrogen bonding between thiophenol produced in the reaction and THF. This was confirmed by measurement of the heat of solution of thiophenol in toluene and THF. Differential scanning calorimetry as well as high temperature calorimetry have been performed on the dimerization and subsequent decarbonylation reactions of PhSMo(CO)3Cp yielding [PhSMo(CO)2Cp]2 and [PhSMo(CO)Cp]2. The enthalpies of reaction of PhSMo(CO)3Cp and [PhSMo(CO)2Cp]2 with PPh3, PPh2Me and P(OMe)3 have also been measured. The disproportionation reaction: 2[PhSMo(CO)2Cp]2 → 2PhSMo(CO)3Cp + [PhSMP(CO)Cp]2 is reported and its enthalpy has also been measured. These data allow determination of the enthalpy of formation of the metal-sulfur clusters [PhSMo(CO)nC5H5]2, n = 1,2.",
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T1 - Heats of reaction of HMo(CO)3(C5R5) (R = H, CH3) with diphenyldisulfide and of formation of the clusters [PhSMo(CO)x(C5H5)]2, x = 1,2. Thermodynamic study of molybdenum-sulfur bond strengths

AU - Mukerjee, Shakti L.

AU - Gonzalez, Alberto A.

AU - Nolan, Steven P.

AU - Ju, Telvin D.

AU - Lang, Russell F.

AU - Hoff, Carl

PY - 1995/1/1

Y1 - 1995/1/1

N2 - The enthalpies of reaction of HMo(CO)3C5R5 (R = H, CH3) with diphenyldisulfide producing PhSMo(CO)3C5R5 and PhSH have been measured in toluene and THF solution (R = H, ΔH= -8.5 ± 0.5 kcal mol-1 (tol), -10.8 ± 0.7 kcal mol-1 (THF); R = CH3, ΔH = -11.3±0.3 kcal mol-1 (tol), -13.2±0.7 kcal mol-1 (THF)). These data are used to estimate the MoSPh bond strength to be on the order of 38-41 kcal mol-1 for these complexes. The increased exothermicity of oxidative addition of disulfide in THF versus toluene is attributed to hydrogen bonding between thiophenol produced in the reaction and THF. This was confirmed by measurement of the heat of solution of thiophenol in toluene and THF. Differential scanning calorimetry as well as high temperature calorimetry have been performed on the dimerization and subsequent decarbonylation reactions of PhSMo(CO)3Cp yielding [PhSMo(CO)2Cp]2 and [PhSMo(CO)Cp]2. The enthalpies of reaction of PhSMo(CO)3Cp and [PhSMo(CO)2Cp]2 with PPh3, PPh2Me and P(OMe)3 have also been measured. The disproportionation reaction: 2[PhSMo(CO)2Cp]2 → 2PhSMo(CO)3Cp + [PhSMP(CO)Cp]2 is reported and its enthalpy has also been measured. These data allow determination of the enthalpy of formation of the metal-sulfur clusters [PhSMo(CO)nC5H5]2, n = 1,2.

AB - The enthalpies of reaction of HMo(CO)3C5R5 (R = H, CH3) with diphenyldisulfide producing PhSMo(CO)3C5R5 and PhSH have been measured in toluene and THF solution (R = H, ΔH= -8.5 ± 0.5 kcal mol-1 (tol), -10.8 ± 0.7 kcal mol-1 (THF); R = CH3, ΔH = -11.3±0.3 kcal mol-1 (tol), -13.2±0.7 kcal mol-1 (THF)). These data are used to estimate the MoSPh bond strength to be on the order of 38-41 kcal mol-1 for these complexes. The increased exothermicity of oxidative addition of disulfide in THF versus toluene is attributed to hydrogen bonding between thiophenol produced in the reaction and THF. This was confirmed by measurement of the heat of solution of thiophenol in toluene and THF. Differential scanning calorimetry as well as high temperature calorimetry have been performed on the dimerization and subsequent decarbonylation reactions of PhSMo(CO)3Cp yielding [PhSMo(CO)2Cp]2 and [PhSMo(CO)Cp]2. The enthalpies of reaction of PhSMo(CO)3Cp and [PhSMo(CO)2Cp]2 with PPh3, PPh2Me and P(OMe)3 have also been measured. The disproportionation reaction: 2[PhSMo(CO)2Cp]2 → 2PhSMo(CO)3Cp + [PhSMP(CO)Cp]2 is reported and its enthalpy has also been measured. These data allow determination of the enthalpy of formation of the metal-sulfur clusters [PhSMo(CO)nC5H5]2, n = 1,2.

KW - Carbonyl complexes

KW - Enthalpy of reaction

KW - Molybdenum complexes

KW - Phenylsulfide complexes

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