Organo f-element thermochemistry. Thorium-Ligand bond disruption enthalpies in tris(cyclopentadienyl)thorium hydrocarbyls

David C. Sonnenberger; Lester R. Morss; Tobin J. Marks

Organo f-element thermochemistry. Thorium-Ligand bond disruption enthalpies in tris(cyclopentadienyl)thorium hydrocarbyls

David C. Sonnenberger, Lester R. Morss, Tobin J. Marks

Northwestern University

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46 Citations (Scopus)

Abstract

Thorium-ligand bond disruption enthalpies (D(Th-R)) have been determined in the series of complexes Cp₃ThR, where Cp = η⁵-C₅H₅ and R = an alkyl group. Thermochemical data were obtained by anaerobic batch-titration solution calorimetry from enthalpies of solution of the Cp₃ThR complexes in toluene followed by enthalpies of alcoholysis with CF₃CH₂OH. D(Th-R)_gas values obtained (2σ) were as follows: CH₂Si(CH₃)₃, 86.1 (3.6) kcal/mol; CH₃, 82.7 (1.1) kcal/mol; CH₂C(CH₃)₃, 77.9 (3.0) kcal/mol; CH₂C₆H₅, 77.9 (2.2) kcal/mol; CH(CH₃)₂, 77.3 (2.7) kcal/mol. These disruption enthalpies parallel but are significantly larger than those for the identical R functionalities in the Cp′ThR₂ series, Cp′ = η⁵-(CH₃)₅C₅.

Original language	English
Pages (from-to)	352-355
Number of pages	4
Journal	Organometallics
Volume	4
Issue number	2
Publication status	Published - 1985

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Inorganic Chemistry
Organic Chemistry

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Sonnenberger, D. C., Morss, L. R., & Marks, T. J. (1985). Organo f-element thermochemistry. Thorium-Ligand bond disruption enthalpies in tris(cyclopentadienyl)thorium hydrocarbyls. Organometallics, 4(2), 352-355.

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title = "Organo f-element thermochemistry. Thorium-Ligand bond disruption enthalpies in tris(cyclopentadienyl)thorium hydrocarbyls",

abstract = "Thorium-ligand bond disruption enthalpies (D(Th-R)) have been determined in the series of complexes Cp3ThR, where Cp = η5-C5H5 and R = an alkyl group. Thermochemical data were obtained by anaerobic batch-titration solution calorimetry from enthalpies of solution of the Cp3ThR complexes in toluene followed by enthalpies of alcoholysis with CF3CH2OH. D(Th-R)gas values obtained (2σ) were as follows: CH2Si(CH3)3, 86.1 (3.6) kcal/mol; CH3, 82.7 (1.1) kcal/mol; CH2C(CH3)3, 77.9 (3.0) kcal/mol; CH2C6H5, 77.9 (2.2) kcal/mol; CH(CH3)2, 77.3 (2.7) kcal/mol. These disruption enthalpies parallel but are significantly larger than those for the identical R functionalities in the Cp′ThR2 series, Cp′ = η5-(CH3)5C5.",

author = "Sonnenberger, {David C.} and Morss, {Lester R.} and Marks, {Tobin J.}",

year = "1985",

language = "English",

volume = "4",

pages = "352--355",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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T1 - Organo f-element thermochemistry. Thorium-Ligand bond disruption enthalpies in tris(cyclopentadienyl)thorium hydrocarbyls

AU - Sonnenberger, David C.

AU - Morss, Lester R.

AU - Marks, Tobin J.

PY - 1985

Y1 - 1985

N2 - Thorium-ligand bond disruption enthalpies (D(Th-R)) have been determined in the series of complexes Cp3ThR, where Cp = η5-C5H5 and R = an alkyl group. Thermochemical data were obtained by anaerobic batch-titration solution calorimetry from enthalpies of solution of the Cp3ThR complexes in toluene followed by enthalpies of alcoholysis with CF3CH2OH. D(Th-R)gas values obtained (2σ) were as follows: CH2Si(CH3)3, 86.1 (3.6) kcal/mol; CH3, 82.7 (1.1) kcal/mol; CH2C(CH3)3, 77.9 (3.0) kcal/mol; CH2C6H5, 77.9 (2.2) kcal/mol; CH(CH3)2, 77.3 (2.7) kcal/mol. These disruption enthalpies parallel but are significantly larger than those for the identical R functionalities in the Cp′ThR2 series, Cp′ = η5-(CH3)5C5.

AB - Thorium-ligand bond disruption enthalpies (D(Th-R)) have been determined in the series of complexes Cp3ThR, where Cp = η5-C5H5 and R = an alkyl group. Thermochemical data were obtained by anaerobic batch-titration solution calorimetry from enthalpies of solution of the Cp3ThR complexes in toluene followed by enthalpies of alcoholysis with CF3CH2OH. D(Th-R)gas values obtained (2σ) were as follows: CH2Si(CH3)3, 86.1 (3.6) kcal/mol; CH3, 82.7 (1.1) kcal/mol; CH2C(CH3)3, 77.9 (3.0) kcal/mol; CH2C6H5, 77.9 (2.2) kcal/mol; CH(CH3)2, 77.3 (2.7) kcal/mol. These disruption enthalpies parallel but are significantly larger than those for the identical R functionalities in the Cp′ThR2 series, Cp′ = η5-(CH3)5C5.

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Organo f-element thermochemistry. Thorium-Ligand bond disruption enthalpies in tris(cyclopentadienyl)thorium hydrocarbyls

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