Advanced search

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

(1991) ORGANOMETALLICS. 10(5). p.1450-1457
Author
Organization
Abstract
Uranium-metal bond disruption enthalpies have been determined in the series of complexes Cp3U-MPh3, where Cp = eta-5-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.
Keywords
METAL-METAL BONDS, HIGHLY REACTIVE ORGANOLANTHANIDES, SILICON-CONTAINING COMPOUNDS, DISSOCIATION ENERGIES, ORGANOMETALLIC COMPOUNDS, CRYSTAL-STRUCTURE, PRIMARY ORGANOSILANES, MOLECULAR-STRUCTURE, AMINE ELIMINATION, HYDRIDE COMPLEXES

Citation

Please use this url to cite or link to this publication:

Chicago
Nolan, Steven, M Porchi, and TJ Marks. 1991. “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.” Organometallics 10 (5): 1450–1457.
APA
Nolan, Steven, Porchi, M., & Marks, T. (1991). 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. ORGANOMETALLICS, 10(5), 1450–1457.
Vancouver
1.
Nolan S, Porchi M, Marks T. 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. ORGANOMETALLICS. 1991;10(5):1450–7.
MLA
Nolan, Steven, M Porchi, and TJ Marks. “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.” ORGANOMETALLICS 10.5 (1991): 1450–1457. Print.
@article{8171498,
  abstract     = {Uranium-metal bond disruption enthalpies have been determined in the series of complexes Cp3U-MPh3, where Cp = eta-5-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 and Porchi, M and Marks, TJ},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  language     = {eng},
  number       = {5},
  pages        = {1450--1457},
  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},
  url          = {http://dx.doi.org/10.1021/om00051a042},
  volume       = {10},
  year         = {1991},
}

Altmetric
View in Altmetric