Heats of reaction of HMo(CO)3C5H5 with CCl4 and CBr4 and of NaMo(CO)3C5H5 with I2 and CH3. Solution thermochemical study of the MoX bond for X = H, Cl, Br, I and CH3

Steven P. Nolan, Ramón López De La Vega, Carl Hoff

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Abstract

The heats of reaction of HMo(CO)3C5H5 with CX4 (X = Cl, Br) producing XMo(CO)3C5H5 have been measured by solution calorimetry and are -31.8±0.9 and -34.4±2.0 kcal/mole, respectively. The heats of reaction of NaMo(CO)3C5H5 with I2 and CH3I producing IMo(CO)3C5H5 and H3CMo(CO)3C5H5 are -32.3± 1.3 and -7.7± 0.3 kcal/mole. Oxidation with Br2CCl4 yielding Br3Mo(CO)2C5H5 was measured for the following complexes: (C5H5(CO)3Mo)2, (-92.0±1.0 kcal/mole), BrMo(CO)3C5H5 (-24.9± 2.0 kcal/mole) and HMo(CO)3C5H5 (-60.7± 2.0 kcal/mole). These and other data are used to calculate the Mo-X bond strength for X = H, Cl, Br, I, and CH3. These bond strength estimates are compared to those reported for X2Mo(C5H5)2. Iodination of H3CMo(CO)3C5H5, reported in the literature to yield CH3I and IMo(CO)3C5H5, actually produces CH3C(O)I and I3Mo(CO)2C5H5.

Original languageEnglish
Pages (from-to)187-199
Number of pages13
JournalJournal of Organometallic Chemistry
Volume315
Issue number2
DOIs
StatePublished - Nov 11 1986

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Carbon Monoxide
Hot Temperature
heat
Calorimetry
Oxidation
heat measurement
oxidation
estimates
Halogenation

ASJC Scopus subject areas

  • Biochemistry
  • Chemical Engineering (miscellaneous)
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Science (miscellaneous)
  • Materials Chemistry

Cite this

Heats of reaction of HMo(CO)3C5H5 with CCl4 and CBr4 and of NaMo(CO)3C5H5 with I2 and CH3. Solution thermochemical study of the MoX bond for X = H, Cl, Br, I and CH3. / Nolan, Steven P.; De La Vega, Ramón López; Hoff, Carl.

In: Journal of Organometallic Chemistry, Vol. 315, No. 2, 11.11.1986, p. 187-199.

Research output: Contribution to journalArticle

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title = "Heats of reaction of HMo(CO)3C5H5 with CCl4 and CBr4 and of NaMo(CO)3C5H5 with I2 and CH3. Solution thermochemical study of the MoX bond for X = H, Cl, Br, I and CH3",
abstract = "The heats of reaction of HMo(CO)3C5H5 with CX4 (X = Cl, Br) producing XMo(CO)3C5H5 have been measured by solution calorimetry and are -31.8±0.9 and -34.4±2.0 kcal/mole, respectively. The heats of reaction of NaMo(CO)3C5H5 with I2 and CH3I producing IMo(CO)3C5H5 and H3CMo(CO)3C5H5 are -32.3± 1.3 and -7.7± 0.3 kcal/mole. Oxidation with Br2CCl4 yielding Br3Mo(CO)2C5H5 was measured for the following complexes: (C5H5(CO)3Mo)2, (-92.0±1.0 kcal/mole), BrMo(CO)3C5H5 (-24.9± 2.0 kcal/mole) and HMo(CO)3C5H5 (-60.7± 2.0 kcal/mole). These and other data are used to calculate the Mo-X bond strength for X = H, Cl, Br, I, and CH3. These bond strength estimates are compared to those reported for X2Mo(C5H5)2. Iodination of H3CMo(CO)3C5H5, reported in the literature to yield CH3I and IMo(CO)3C5H5, actually produces CH3C(O)I and I3Mo(CO)2C5H5.",
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T1 - Heats of reaction of HMo(CO)3C5H5 with CCl4 and CBr4 and of NaMo(CO)3C5H5 with I2 and CH3. Solution thermochemical study of the MoX bond for X = H, Cl, Br, I and CH3

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N2 - The heats of reaction of HMo(CO)3C5H5 with CX4 (X = Cl, Br) producing XMo(CO)3C5H5 have been measured by solution calorimetry and are -31.8±0.9 and -34.4±2.0 kcal/mole, respectively. The heats of reaction of NaMo(CO)3C5H5 with I2 and CH3I producing IMo(CO)3C5H5 and H3CMo(CO)3C5H5 are -32.3± 1.3 and -7.7± 0.3 kcal/mole. Oxidation with Br2CCl4 yielding Br3Mo(CO)2C5H5 was measured for the following complexes: (C5H5(CO)3Mo)2, (-92.0±1.0 kcal/mole), BrMo(CO)3C5H5 (-24.9± 2.0 kcal/mole) and HMo(CO)3C5H5 (-60.7± 2.0 kcal/mole). These and other data are used to calculate the Mo-X bond strength for X = H, Cl, Br, I, and CH3. These bond strength estimates are compared to those reported for X2Mo(C5H5)2. Iodination of H3CMo(CO)3C5H5, reported in the literature to yield CH3I and IMo(CO)3C5H5, actually produces CH3C(O)I and I3Mo(CO)2C5H5.

AB - The heats of reaction of HMo(CO)3C5H5 with CX4 (X = Cl, Br) producing XMo(CO)3C5H5 have been measured by solution calorimetry and are -31.8±0.9 and -34.4±2.0 kcal/mole, respectively. The heats of reaction of NaMo(CO)3C5H5 with I2 and CH3I producing IMo(CO)3C5H5 and H3CMo(CO)3C5H5 are -32.3± 1.3 and -7.7± 0.3 kcal/mole. Oxidation with Br2CCl4 yielding Br3Mo(CO)2C5H5 was measured for the following complexes: (C5H5(CO)3Mo)2, (-92.0±1.0 kcal/mole), BrMo(CO)3C5H5 (-24.9± 2.0 kcal/mole) and HMo(CO)3C5H5 (-60.7± 2.0 kcal/mole). These and other data are used to calculate the Mo-X bond strength for X = H, Cl, Br, I, and CH3. These bond strength estimates are compared to those reported for X2Mo(C5H5)2. Iodination of H3CMo(CO)3C5H5, reported in the literature to yield CH3I and IMo(CO)3C5H5, actually produces CH3C(O)I and I3Mo(CO)2C5H5.

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