Open AccessAlkyl-metal and aryl-metal bond chemistry in coordinately unsaturated polynuclear metal complexes
Author(s) -
Günter Schmidt,
E. L. Muetterties,
M. A. Beno,
Jack M. Williams
Publication year - 1981
Publication title -
proceedings of the national academy of sciences of the united states of america
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.011
H-Index - 771
eISSN - 1091-6490
pISSN - 0027-8424
DOI - 10.1073/pnas.78.3.1318
Subject(s) - chemistry , aryl , iridium , hydride , cyclooctadiene , reductive elimination , medicinal chemistry , rhodium , alkyl , bond cleavage , dimer , metal , oxidative addition , 1,5 cyclooctadiene , stereochemistry , organic chemistry , catalysis
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°C. The x-ray crystal structure of [μ-CH3 Rh (1,5-cyclooctadiene)]2 is reported. The analogous iridium dimer decomposes by an initial sequence of α-hydrogen abstraction and then reductive elimination of hydrogen to give [μ-CH2 Ir(1,5-cyclooctadiene)]2 . Formed in high yield by the decomposition of the ethylrhodium complex was [HRh(C8 H11 )]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.