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New stoichiometric and catalytic organometallic chemistry with actinides. CH activation and phosphine/phosphite coordination chemistry

Authors
Journal
Inorganica Chimica Acta
0020-1693
Publisher
Elsevier
Publication Date
Volume
94
Issue
5
Identifiers
DOI: 10.1016/s0020-1693(00)87455-1
Disciplines
  • Chemistry
  • Design

Abstract

Abstract This short review highlights two areas of recent activity in organoactinide chemistry: actinide-centered homogeneous chemistry in which intra- and intermolecular CH activation takes place on hydrocarbon fragments, and actinide coordination chemistry involving phosphine and phosphite ligands. It is shown that new metal-ligand bond enthalpy data afford a far greater understanding of observed CH activation patterns, and, moreover, support the design of successful new strategies for CH activation on exogenous hydrocarbon molecules. For example, the strain energy of a thoracyclobutane provides the driving force for ring-opening reactions that involve attack on a alkane or arene carbon-hydrogen bond. While phosphines have been shown to be rather unexceptional ligands for organoactinides, the reaction of trialkylphosphites with the organoactinide hydrides {M[(CH 3) 5C 5] 2H 2} 2, M = Th, U takes a different course. In the case of P(OCH 3) 3, quantitative demethoxylation of the phosphite occurs under mild conditions to yield μ-phosphinidine complexes of the type {M[(CH 3) 5C 5] 2(OCH 3)}PH.

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