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Mechanistic Aspects of Hydrosilylation Catalyzed by (ArN=)Mo(H)(Cl)(PMe3)3

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Chemistry Department, Brock University, 500 Glenridge Avenue, St. Catharines, Ontario L2S 3A1, Canada
N.S. Kurnakov Institute of General and Inorganic Chemistry, 31 Leninskii Prospekt, Moscow, 119991, Russia
§ Chemistry Department, University of Durham, South Road, Durham DH1 3LE, United Kingdom
*E-mail: [email protected]. Phone: (+1)905 688-5550, ext. 3350.
Cite this: Inorg. Chem. 2012, 51, 7, 4300–4313
Publication Date (Web):March 21, 2012
Copyright © 2012 American Chemical Society

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    Abstract Image

    The reaction of (ArN=)MoCl2(PMe3)3 (Ar = 2,6-diisopropylphenyl) with L-Selectride gives the hydrido-chloride complex (ArN=)Mo(H)(Cl)(PMe3)3 (2). Complex 2 was found to catalyze the hydrosilylation of carbonyls and nitriles as well as the dehydrogenative silylation of alcohols and water. Compound 2 does not show any productive reaction with PhSiH3; however, a slow H/D exchange and formation of (ArN=)Mo(D)(Cl)(PMe3)3 (2D) was observed upon addition of PhSiD3. Reactivity of 2 toward organic substrates was studied. Stoichiometric reactions of 2 with benzaldehyde and cyclohexanone start with dissociation of the trans-to-hydride PMe3 ligand followed by coordination and insertion of carbonyls into the Mo–H bond to form alkoxy derivatives (ArN=)Mo(Cl)(OR)(PMe2)L2 (3: R = OCH2Ph, L2 = 2 PMe3; 5: R = OCH2Ph, L2 = η2-PhC(O)H; 6: R = OCy, L2 = 2 PMe3). The latter species reacts with PhSiH3 to furnish the corresponding silyl ethers and to recover the hydride 2. An analogous mechanism was suggested for the dehydrogenative ethanolysis with PhSiH3, with the key intermediate being the ethoxy complex (ArN=)Mo(Cl)(OEt)(PMe3)3 (7). In the case of hydrosilylation of acetophenone, a D-labeling experiment, i.e., a reaction of 2 with acetophenone and PhSiD3 in the 1:1:1 ratio, suggests an alternative mechanism that does not involve the intermediacy of an alkoxy complex. In this particular case, the reaction presumably proceeds via Lewis acid catalysis. Similar to the case of benzaldehyde, treatment of 2 with styrene gives trans-(ArN=)Mo(H)(η2-CH2═CHPh)(PMe3)2 (8). Complex 8 slowly decomposes via the release of ethylbenzene, indicating only a slow insertion of styrene ligand into the Mo–H bond of 8.

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    X-ray crystallographic data in CIF format for the structure determinations for complexes 1 and 6, kinetic plots, and selected NMR data. This material is available free of charge via the Internet at

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