| Popis: |
This short review highlights two areas of recent activity in organoactinide chemistry: actinide-centered homogeneous chemistry in which intra- and intermolecular CH 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 CH activation patterns, and, moreover, support the design of successful new strategies for CH 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[(CH3)5C5]2H2}2, M = Th, U takes a different course. In the case of P(OCH3)3, quantitative demethoxylation of the phosphite occurs under mild conditions to yield μ-phosphinidine complexes of the type {M[(CH3)5C5]2(OCH3)}PH. |
