A new class of coordinately unsaturated polynuclear rhodium and iridium alkyl, benzyl, and aryl derivatives of the form [RM(1,5-cyclooctadiene)](x) have been prepared by the reaction of the organolithium reagent with the cyclooctadienemetal chlorides at -78 degrees C. The x-ray crystal structure of [mu-CH(3)Rh (1,5-cyclooctadiene)](2) is reported. The analogous iridium dimer decomposes by an initial sequence of alpha-hydrogen abstraction and then reductive elimination of hydrogen to give [mu-CH(2)Ir(1,5-cyclooctadiene)](2). Formed in high yield by the decomposition of the ethylrhodium complex was [HRh(C(8)H(11))](4), a tetrahedral cluster with face-bridging hydride ligands. Also discussed are the reactivities of the benzyl and phenyl derivatives. Unique reaction pathways for C-H bond activation and scission in this chemistry are delineated.
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| http://dx.doi.org/10.1073/pnas.78.3.1318 | DOI Listing |
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