The heat of reaction of EtMo(CO)3C5H5 and HMo(CO)3C5H5 and related reactions. Thermochemical study of reductive elimination in alkyl molybdenum complexes

Steven P. Nolan, Ramon Lopez De La Vega, Shakti L. Mukerjee, Alberto A. Gonzalez, Kai Zhang, Carl Hoff

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Abstract

The enthalpies of the following reactions have been measured by solution calorimetry: HMo(CO)3C5H5+EtMo(CO)3C5 H5 →EtC(O)H+ 1 2[Mo(CO)2C5H5]2+ 1 2[Mo(CO)3C5H5]2 [Mo(CO)2C5H5]2+2PR 3→[Mo(CO)2(PR3) C5H5]2 PR3 = P(OMe)3 and P(C6H5)2Me RMo(CO)3C5H5+I2→R;I+IMo(CO)3C5H5 R = C6H5CH2, H2CCHCH2 R = Mo(CO)3C5H5+PR3→RC(O)Mo (CO)2(PR3)C5H5 R = C6H5CH2 PR3 = PMe3, PMe2Ph, PMePh2, PPh3, P(OMe)3. The results from this work are combined with earlier data to generate estimates for MoX bond strengths (X = H, Cl, Br, I, CH3, C2H5, C3H5 and PhCH 2). The influence of phosphine substitution on the thermochemistry of model catalytic reactions is discussed.

Original languageEnglish
Pages (from-to)1491-1498
Number of pages8
JournalPolyhedron
Volume7
Issue number16-17
DOIs
StatePublished - Jan 1 1988

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Calorimetry
Molybdenum
molybdenum
elimination
heat measurement
Hot Temperature
heat
phosphine
Thermochemistry
thermochemistry
phosphines
Enthalpy
Substitution reactions
enthalpy
substitutes

ASJC Scopus subject areas

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

Cite this

The heat of reaction of EtMo(CO)3C5H5 and HMo(CO)3C5H5 and related reactions. Thermochemical study of reductive elimination in alkyl molybdenum complexes. / Nolan, Steven P.; La Vega, Ramon Lopez De; Mukerjee, Shakti L.; Gonzalez, Alberto A.; Zhang, Kai; Hoff, Carl.

In: Polyhedron, Vol. 7, No. 16-17, 01.01.1988, p. 1491-1498.

Research output: Contribution to journalArticle

Nolan, Steven P. ; La Vega, Ramon Lopez De ; Mukerjee, Shakti L. ; Gonzalez, Alberto A. ; Zhang, Kai ; Hoff, Carl. / The heat of reaction of EtMo(CO)3C5H5 and HMo(CO)3C5H5 and related reactions. Thermochemical study of reductive elimination in alkyl molybdenum complexes. In: Polyhedron. 1988 ; Vol. 7, No. 16-17. pp. 1491-1498.
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title = "The heat of reaction of EtMo(CO)3C5H5 and HMo(CO)3C5H5 and related reactions. Thermochemical study of reductive elimination in alkyl molybdenum complexes",
abstract = "The enthalpies of the following reactions have been measured by solution calorimetry: HMo(CO)3C5H5+EtMo(CO)3C5 H5 →EtC(O)H+ 1 2[Mo(CO)2C5H5]2+ 1 2[Mo(CO)3C5H5]2 [Mo(CO)2C5H5]2+2PR 3→[Mo(CO)2(PR3) C5H5]2 PR3 = P(OMe)3 and P(C6H5)2Me RMo(CO)3C5H5+I2→R;I+IMo(CO)3C5H5 R = C6H5CH2, H2CCHCH2 R = Mo(CO)3C5H5+PR3→RC(O)Mo (CO)2(PR3)C5H5 R = C6H5CH2 PR3 = PMe3, PMe2Ph, PMePh2, PPh3, P(OMe)3. The results from this work are combined with earlier data to generate estimates for MoX bond strengths (X = H, Cl, Br, I, CH3, C2H5, C3H5 and PhCH 2). The influence of phosphine substitution on the thermochemistry of model catalytic reactions is discussed.",
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T1 - The heat of reaction of EtMo(CO)3C5H5 and HMo(CO)3C5H5 and related reactions. Thermochemical study of reductive elimination in alkyl molybdenum complexes

AU - Nolan, Steven P.

AU - La Vega, Ramon Lopez De

AU - Mukerjee, Shakti L.

AU - Gonzalez, Alberto A.

AU - Zhang, Kai

AU - Hoff, Carl

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N2 - The enthalpies of the following reactions have been measured by solution calorimetry: HMo(CO)3C5H5+EtMo(CO)3C5 H5 →EtC(O)H+ 1 2[Mo(CO)2C5H5]2+ 1 2[Mo(CO)3C5H5]2 [Mo(CO)2C5H5]2+2PR 3→[Mo(CO)2(PR3) C5H5]2 PR3 = P(OMe)3 and P(C6H5)2Me RMo(CO)3C5H5+I2→R;I+IMo(CO)3C5H5 R = C6H5CH2, H2CCHCH2 R = Mo(CO)3C5H5+PR3→RC(O)Mo (CO)2(PR3)C5H5 R = C6H5CH2 PR3 = PMe3, PMe2Ph, PMePh2, PPh3, P(OMe)3. The results from this work are combined with earlier data to generate estimates for MoX bond strengths (X = H, Cl, Br, I, CH3, C2H5, C3H5 and PhCH 2). The influence of phosphine substitution on the thermochemistry of model catalytic reactions is discussed.

AB - The enthalpies of the following reactions have been measured by solution calorimetry: HMo(CO)3C5H5+EtMo(CO)3C5 H5 →EtC(O)H+ 1 2[Mo(CO)2C5H5]2+ 1 2[Mo(CO)3C5H5]2 [Mo(CO)2C5H5]2+2PR 3→[Mo(CO)2(PR3) C5H5]2 PR3 = P(OMe)3 and P(C6H5)2Me RMo(CO)3C5H5+I2→R;I+IMo(CO)3C5H5 R = C6H5CH2, H2CCHCH2 R = Mo(CO)3C5H5+PR3→RC(O)Mo (CO)2(PR3)C5H5 R = C6H5CH2 PR3 = PMe3, PMe2Ph, PMePh2, PPh3, P(OMe)3. The results from this work are combined with earlier data to generate estimates for MoX bond strengths (X = H, Cl, Br, I, CH3, C2H5, C3H5 and PhCH 2). The influence of phosphine substitution on the thermochemistry of model catalytic reactions is discussed.

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