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 language | English |
|---|---|
| Pages (from-to) | 1450-1457 |
| Number of pages | 8 |
| Journal | Organometallics |
| Volume | 10 |
| Issue number | 5 |
| Publication status | Published - 1991 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
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. / Nolan, Steven P.; Porchia, Marina; Marks, Tobin J.
In: Organometallics, Vol. 10, No. 5, 1991, p. 1450-1457.Research output: Contribution to journal › Article
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TY - JOUR
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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M3 - Article
VL - 10
SP - 1450
EP - 1457
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 5
ER -