A kinetic, mechanistic, and molecular mechanics investigation of olefin insertion into organoactinide-hydride bonds. Metal, olefin, ancillary ligand, and diastereoselection effects

Journal Article · Wed Jul 04 04:00:00 EDT 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00170a015· OSTI ID:6660505

Lin, Zerong; Marks, T J ^[1]

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1. Northwestern Univ., Evanston, IL (USA)

This contribution reports a kinetic/mechanistic/stereochemical/molecular mechanics study of olefin insertion into the actinide-hydrogen bonds of Cp{prime}{sub 2}An(H)(OR) complexes (Cp{prime} = {eta}{sup 5}-(CH{sub 3}){sub 5}C{sub 5}; An = Th, U; R = achiral or chiral alkyl group). For the reaction Cp{prime}{sub 2}An(H)(O-t-Bu) + cyclohexene (An = Th), the rate law is first order in organoactinide and first order in olefin. For Cp{prime}{sub 2}Th(H)(OCH(t-Bu){sub 2}) + 1-hexene, k{sub Th{minus}H}/k{sub Th{minus}D} = 1.3 (2). A molecular mechanics/ molecular graphics analysis suggests that the sterically most favorable direction of olefin approach toward the actinide center is between the U-H and U-O bonds rather than from the side. These results provide additional insight into ancillary ligand effects on the kinetics of organo-f-element-catalyzed olefin hydrogenation.

• OSTI ID: 6660505
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:14; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTINIDE COMPLEXES
ALKENES
CHEMICAL ACTIVATION
COMPLEXES
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
KINETICS
MATHEMATICAL MODELS
MEASURING INSTRUMENTS
MEASURING METHODS
MECHANICS
MOLECULAR MODELS
NUMERICAL DATA
ORGANIC COMPOUNDS
THORIUM COMPLEXES
URANIUM COMPLEXES