Organo f-Element Thermochemistry. Thorium-Ligand Bond Disruption Enthalpies in Tris(cyclopentadienyl)thorium Hydrocarbyls

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

doi:10.1021/om00121a028

Organo f-Element Thermochemistry. Thorium-Ligand Bond Disruption Enthalpies in Tris(cyclopentadienyl)thorium Hydrocarbyls

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

Northwestern University

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

46 Citations (Scopus)

Abstract

Thorium-ligand bond disruption enthalpies (D(Th-R)) have been determined in the series of complexes Cp₃ThR, where Cp = η⁵-C₅Hg₅ 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'₂ThR₂ series, Cp' = η⁵-(CH₃)₅C₅.

Original language	English
Pages (from-to)	352-355
Number of pages	4
Journal	Organometallics
Volume	4
Issue number	2
DOIs	https://doi.org/10.1021/om00121a028
Publication status	Published - Feb 1985

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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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-C5Hg5 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'2ThR2 series, Cp' = η5-(CH3)5C5.",

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

year = "1985",

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AU - Marks, Tobin J.

AU - Morss, Lester R.

PY - 1985/2

Y1 - 1985/2

N2 - Thorium-ligand bond disruption enthalpies (D(Th-R)) have been determined in the series of complexes Cp3ThR, where Cp = η5-C5Hg5 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'2ThR2 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-C5Hg5 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'2ThR2 series, Cp' = η5-(CH3)5C5.

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Organo f-Element Thermochemistry. Thorium-Ligand Bond Disruption Enthalpies in Tris(cyclopentadienyl)thorium Hydrocarbyls

Abstract

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