Organo-f-Element Thermochemistry. Actiniae-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*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

114 Scopus citations

Abstract

Uranium-metal bond disruption enthalpies have been determined in the series of complexes Cp3U−MPh3, where Cp = η6−C6H6, 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 (US)
Pages (from-to)1450-1457
Number of pages8
JournalOrganometallics
Volume10
Issue number5
DOIs
StatePublished - May 1 1991

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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