Dinuclear elimination as a route to unusual bridging carbonyls and acetyls in heterobimetallic complexes

Journal Article · Tue Nov 16 23:00:00 EST 1982 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00387a034· OSTI ID:5485822

Marsella, J A ^[1]; Huffman, J C; Caulton, K G; Longato, B; Norton, J R

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1. Indiana Univ., Bloomington

Reaction of Cp/sub 2/ZrMe/sub 2/ with CpMo(CO)/sub 3/H yields methane and Cp/sub 2/ZrMeMo(CO)/sub 3/Cp (1), which has two terminal carbonyl ligands and a third carbonyl with a low (1545 cm/sup -1/) stretching frequency. Added gaseous CO inserts into the Zr-Me bond in 1 to form the eta/sup 2/-acetyl ligand in 2, Cp/sub 2/Zr(C(O)Me)(OC)Mo(CO)/sub 2/Cp, which is shown by X-ray crystallography to lack a Zr-Mo bond but to be held together by a carbonyl-OC bridge. Complex 2, which is also formed from Cp/sub 2/Zr(C(O)Me)Me and CpMo(CO)/sub 3/H, reacts rapidly with proton sources to form CpMo(CO)/sub 3/H and CH/sub 3/CHO. Complex 2 slowly loses CO in solution to form Cp/sub 2/Zr(OCMe)(OC)MoCOCp, which contains a Zr-Mo bond, a bridging oxycarbene/acetyl, and a four-electron-donor carbonyl.

• OSTI ID: 5485822
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 104:23; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
BOND ANGLE
BOND LENGTHS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
CYCLOALKENES
CYCLOPENTADIENE
DIENES
DIMENSIONS
HYDROCARBONS
KINETICS
LENGTH
MOLYBDENUM COMPLEXES
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
POLYENES
REACTION KINETICS
REDUCTION
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
ZIRCONIUM COMPLEXES