Alkyl-metal and aryl-metal bond chemistry in coordinately unsaturated polynuclear metal complexes

Journal Article · Sun Mar 01 04:00:00 EST 1981 · Proc. Natl. Acad. Sci. U.S.A.; (United States)

DOI:https://doi.org/10.1073/pnas.78.3.1318· OSTI ID:6508094

Schmidt, G F ^[1]; Muetterties, E L; Beno, M A; Williams, J M

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1. Univ. of California, Berkeley

A new class of coordinately unsaturated polynuclear rhodium and iridium alkyl, benzyl, and aryl derivatives of the form (RM(1,5-cyclooctadiene))/sub x/ have been prepared by the reaction of the organolithium reagent with the cyclooctadiene-metal chlorides at -78/sup 0/C. The x-ray crystal structure of (..mu..-CH/sub 3/Rh(1,5-cyclooctadiene))/sub 2/ is reported. The analogous iridium dimer decomposes by an initial sequence of ..cap alpha..-hydrogen abstraction and then reductive elimination of hydrogen to give (..mu..-CH/sub 2/Ir(1,5-cyclooctadiene))/sub 2/. Formed in high yield by the decomposition of the ethylrhodium complex was (HRh(C/sub 8/H/sub 11/))/sub 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.

• OSTI ID: 6508094
• Journal Information: Proc. Natl. Acad. Sci. U.S.A.; (United States), Journal Name: Proc. Natl. Acad. Sci. U.S.A.; (United States) Vol. 78:3; ISSN PNASA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
ALKALI METALS
BINDING ENERGY
CHEMICAL BONDS
CHEMICAL COMPOSITION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
COMPLEXOMETRY
COORDINATION VALENCES
DECOMPOSITION
DIMERS
ELEMENTS
ENERGY
IRIDIUM COMPLEXES
KINETICS
LITHIUM
METALS
REACTION KINETICS
RHODIUM COMPLEXES
SATURATION
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
VALENCE