Oxidative Reactions of the MoIV Dialkyl Complex [{(3‐CF3C6H4NCH2CH2)2NMe}Mo(CH2SiMe3)2] |
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| Authors: | Adam S Hock Dr Richard R Schrock Prof |
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| Institution: | Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA, Fax: (+1)?617‐253‐7670 |
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| Abstract: | The structure of (CF3N2NMe)Mo(CH2SiMe3)2] (in which (CF3N2NMe)2? is (3‐CF3C6H4NCH2CH2)2NMe]2?) is approximately trigonal bipyramidal with one axial and one equatorial alkyl ligand. Heating of solutions of (CF3N2NMe)Mo(CH2SiMe3)2] in D6]benzene in the presence of five equivalents of 2‐butyne led to diamagnetic (CF3N2NMe)Mo(CHSiMe3)(η2‐MeC?CMe)], whose structure is approximately square pyramidal with the alkyne occupying the axial site. Addition of one equivalent of cyclohexene sulfide to (CF3N2NMe)Mo(CH2SiMe3)2] at room temperature produced the diamagnetic, dimeric molybdenum(IV) sulfido complex, {(CF3N2NMe)MoS}2]. This complex is composed of two approximately trigonal bipyramidal centers, each containing one axial and one equatorial sulfur atom. Oxidation of (CF3N2NMe)Mo(CH2SiMe3)2] with hexachloroethane resulted in formation of tetramethylsilane, HCl, and the sparingly soluble, red alkylidyne complex, {(CF3N2NMe)Mo(CSiMe3)Cl}2]. This complex forms a dimer through bridging chlorides. The oxidation reactions of (CF3N2NMe)Mo(CH2SiMe3)2] with 2‐butyne, cyclohexene sulfide, or C2Cl6 are all proposed to proceed by α‐hydrogen abstraction in the MoVI species to yield (initially) the Mo?CHSiMe3 species and tetramethylsilane. |
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| Keywords: | alkylidenes alpha abstraction molybdenum oxidation structure elucidation |
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