Hock Adam S, Schrock Richard R
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Chem Asian J. 2007 Jul 2;2(7):867-74. doi: 10.1002/asia.200700093.
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)(eta(2)-MeC[triple bond]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 alpha-hydrogen abstraction in the Mo(VI) species to yield (initially) the Mo=CHSiMe3 species and tetramethylsilane.
[(CF3N2NMe)Mo(CH2SiMe3)2]（其中(CF3N2NMe)2-为[(3-CF3C6H4NCH2CH2)2NMe]2-）的结构近似为三角双锥，有一个轴向和一个赤道面烷基配体。在五当量2-丁炔存在下，[(CF3N2NMe)Mo(CH2SiMe3)2]在[D6]苯中的溶液加热后生成抗磁性的[(CF3N2NMe)Mo(CHSiMe3)(η(2)-MeC≡CMe)]，其结构近似为方锥，炔烃占据轴向位置。室温下向[(CF3N2NMe)Mo(CH2SiMe3)2]中加入一当量环己烯硫醚，生成抗磁性的二聚钼(IV)硫代配合物[{(CF3N2NMe)MoS}2]。该配合物由两个近似三角双锥中心组成，每个中心含有一个轴向和一个赤道面硫原子。[(CF3N2NMe)Mo(CH2SiMe3)2]与六氯乙烷氧化反应生成四甲基硅烷、HCl和微溶的红色亚烷基配合物[{(CF3N2NMe)Mo(CSiMe3)Cl}2]。该配合物通过桥连氯原子形成二聚体。[(CF3N2NMe)Mo(CH2SiMe3)2]与2-丁炔、环己烯硫醚或C2Cl6的氧化反应均被认为是通过Mo(VI)物种中的α-氢提取（最初）生成Mo=CHSiMe3物种和四甲基硅烷。
