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 D. Hoff

doi:10.1016/0022-328X(86)80437-5

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 D. Hoff

Chemistry

Research output: Contribution to journal › Article › peer-review

21 Scopus citations

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 language	English (US)
Pages (from-to)	187-199
Number of pages	13
Journal	Journal of Organometallic Chemistry
Volume	315
Issue number	2
DOIs	https://doi.org/10.1016/0022-328X(86)80437-5
State	Published - Nov 11 1986

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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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 D.

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

Research output: Contribution to journal › Article › peer-review

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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.",

author = "Nolan, {Steven P.} and {De La Vega}, {Ram{\'o}n L{\'o}pez} and Hoff, {Carl D.}",

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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

AU - Nolan, Steven P.

AU - De La Vega, Ramón López

AU - Hoff, Carl D.

PY - 1986/11/11

Y1 - 1986/11/11

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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