Organo-f-element thermochemistry. Actinide-group 14 element and actinide-transition-element bond disruption enthalpies and stoichiometric/catalytic chemical implications thereof in heterobimetallic tris(cyclopentadienyl)uranium(IV) compounds

Steven P. Nolan, Marina Porchia, Tobin J Marks

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Abstract

Uranium-metal bond disruption enthalpies have been determined in the series of complexes Cp3U-MPh3, where Cp = η5-C5H5, Ph = C6H5, and M = Si, Ge, Sn, and in Cp3U-M′(CO)2Cp, where M′ = Fe, Ru. Thermochemical data were obtained by anaerobic batch-titration solution calorimetry in toluene from enthalpies of solution and iodinolysis of the aforementioned compounds. Derived U-M/U-M′ bond disruption enthalpies in toluene solution are as follows (M/M′ moiety, kcal/mol): SiPh3,37.3 (4.2); GePh3, 38.9 (4.5); SnPh3, 37.2 (4.0); Fe(CO)2Cp, 30.9 (3.0); Ru(CO)2Cp, 40.4 (4.0). These data fall in a relatively narrow range and indicate comparatively weak heterobimetallic bonding. Chemical implications of the present thermochemical results include the general favorability and marked M/M′ sensitivity of alkane, hydrogen, and amine elimination synthetic routes to these compounds, the existence of favorable pathways for hydrocarbon and olefin activation, and the observation that no steps in plausible f-element-catalyzed dehydrogenative silane polymerization and olefin hydrosilylation cycles are predicted to have major thermodynamic impediments.

Original languageEnglish
Pages (from-to)1450-1457
Number of pages8
JournalOrganometallics
Volume10
Issue number5
Publication statusPublished - 1991

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Transition Elements
Actinoid Series Elements
Thermochemistry
Uranium
thermochemistry
Carbon Monoxide
uranium
Enthalpy
enthalpy
transition metals
Toluene
Alkenes
alkenes
toluene
Hydrosilylation
Silanes
Alkanes
Calorimetry
Hydrocarbons
Titration

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

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title = "Organo-f-element thermochemistry. Actinide-group 14 element and actinide-transition-element bond disruption enthalpies and stoichiometric/catalytic chemical implications thereof in heterobimetallic tris(cyclopentadienyl)uranium(IV) compounds",
abstract = "Uranium-metal bond disruption enthalpies have been determined in the series of complexes Cp3U-MPh3, where Cp = η5-C5H5, Ph = C6H5, and M = Si, Ge, Sn, and in Cp3U-M′(CO)2Cp, where M′ = Fe, Ru. Thermochemical data were obtained by anaerobic batch-titration solution calorimetry in toluene from enthalpies of solution and iodinolysis of the aforementioned compounds. Derived U-M/U-M′ bond disruption enthalpies in toluene solution are as follows (M/M′ moiety, kcal/mol): SiPh3,37.3 (4.2); GePh3, 38.9 (4.5); SnPh3, 37.2 (4.0); Fe(CO)2Cp, 30.9 (3.0); Ru(CO)2Cp, 40.4 (4.0). These data fall in a relatively narrow range and indicate comparatively weak heterobimetallic bonding. Chemical implications of the present thermochemical results include the general favorability and marked M/M′ sensitivity of alkane, hydrogen, and amine elimination synthetic routes to these compounds, the existence of favorable pathways for hydrocarbon and olefin activation, and the observation that no steps in plausible f-element-catalyzed dehydrogenative silane polymerization and olefin hydrosilylation cycles are predicted to have major thermodynamic impediments.",
author = "Nolan, {Steven P.} and Marina Porchia and Marks, {Tobin J}",
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T1 - Organo-f-element thermochemistry. Actinide-group 14 element and actinide-transition-element bond disruption enthalpies and stoichiometric/catalytic chemical implications thereof in heterobimetallic tris(cyclopentadienyl)uranium(IV) compounds

AU - Nolan, Steven P.

AU - Porchia, Marina

AU - Marks, Tobin J

PY - 1991

Y1 - 1991

N2 - Uranium-metal bond disruption enthalpies have been determined in the series of complexes Cp3U-MPh3, where Cp = η5-C5H5, Ph = C6H5, and M = Si, Ge, Sn, and in Cp3U-M′(CO)2Cp, where M′ = Fe, Ru. Thermochemical data were obtained by anaerobic batch-titration solution calorimetry in toluene from enthalpies of solution and iodinolysis of the aforementioned compounds. Derived U-M/U-M′ bond disruption enthalpies in toluene solution are as follows (M/M′ moiety, kcal/mol): SiPh3,37.3 (4.2); GePh3, 38.9 (4.5); SnPh3, 37.2 (4.0); Fe(CO)2Cp, 30.9 (3.0); Ru(CO)2Cp, 40.4 (4.0). These data fall in a relatively narrow range and indicate comparatively weak heterobimetallic bonding. Chemical implications of the present thermochemical results include the general favorability and marked M/M′ sensitivity of alkane, hydrogen, and amine elimination synthetic routes to these compounds, the existence of favorable pathways for hydrocarbon and olefin activation, and the observation that no steps in plausible f-element-catalyzed dehydrogenative silane polymerization and olefin hydrosilylation cycles are predicted to have major thermodynamic impediments.

AB - Uranium-metal bond disruption enthalpies have been determined in the series of complexes Cp3U-MPh3, where Cp = η5-C5H5, Ph = C6H5, and M = Si, Ge, Sn, and in Cp3U-M′(CO)2Cp, where M′ = Fe, Ru. Thermochemical data were obtained by anaerobic batch-titration solution calorimetry in toluene from enthalpies of solution and iodinolysis of the aforementioned compounds. Derived U-M/U-M′ bond disruption enthalpies in toluene solution are as follows (M/M′ moiety, kcal/mol): SiPh3,37.3 (4.2); GePh3, 38.9 (4.5); SnPh3, 37.2 (4.0); Fe(CO)2Cp, 30.9 (3.0); Ru(CO)2Cp, 40.4 (4.0). These data fall in a relatively narrow range and indicate comparatively weak heterobimetallic bonding. Chemical implications of the present thermochemical results include the general favorability and marked M/M′ sensitivity of alkane, hydrogen, and amine elimination synthetic routes to these compounds, the existence of favorable pathways for hydrocarbon and olefin activation, and the observation that no steps in plausible f-element-catalyzed dehydrogenative silane polymerization and olefin hydrosilylation cycles are predicted to have major thermodynamic impediments.

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