Adams Richard D, Kwon O-Sung
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, USA.
Inorg Chem. 2003 Oct 6;42(20):6175-82. doi: 10.1021/ic030077z.
Reaction of CpMoMn(CO)(8) with elemental selenium and Me(3)NO in the absence of light yielded the diselenido complex CpMoMn(CO)(5)(mu-Se(2)), 2. Compound 2 contains a bridging diselenido ligand lying perpendicular to the Mo-Mn bond, Mo-Mn = 2.8421(10) A. In the presence of room light, the reaction yielded the tetranuclear metal complex Cp(2)Mo(2)Mn(2)(CO)(7)(mu(3)-Se)(4), 3 (36% yield), and 2 (7% yield). Compound 2 reacted with ethylene to yield the ethanediselenato complex CpMoMn(CO)(5)(mu-SeCH(2)CH(2)Se), 4, by insertion of ethylene into the Se-Se bond. Compound 2 also reacted with (PPh(3))(2)Pt(PhC(2)Ph) and CpCo(CO)(2) to yield the complexes CpMoMnPt(PPh(3))(2)(CO)(5)(mu(3)-Se)(2), 5, and Cp(2)CoMoMn(CO)(5)(mu(3)-Se)(2), 6, respectively, by insertion of the metal groupings CpCo and Pt(PPh(3))(2) into the Se-Se bond of 2. The oxo compound Cp(2)CoMo(O)Mn(CO)(5)(mu(3)-Se)(2), 7, was obtained from 6 by decarbonylation at molybdenum by using Me(3)NO. The molecular structures of the complexes 2-7 were established by single-crystal X-ray diffraction analyses.
在无光条件下，CpMoMn(CO)(8) 与元素硒和 Me(3)NO 反应生成二硒化物配合物 CpMoMn(CO)(5)(μ-Se(2))，即化合物 2。化合物 2 含有一个垂直于 Mo-Mn 键的桥连二硒化物配体，Mo-Mn = 2.8421(10) Å。在室内光存在的情况下，该反应生成四核金属配合物 Cp(2)Mo(2)Mn(2)(CO)(7)(μ(3)-Se)(4)，即化合物 3（产率 36%）和化合物 2（产率 7%）。化合物 2 与乙烯反应，通过乙烯插入 Se-Se 键生成乙二硒酸根配合物 CpMoMn(CO)(5)(μ-SeCH(2)CH(2)Se)，即化合物 4。化合物 2 还分别与 (PPh(3))(2)Pt(PhC(2)Ph) 和 CpCo(CO)(2) 反应，通过将金属基团 CpCo 和 Pt(PPh(3))(2) 插入化合物 2 的 Se-Se 键，生成配合物 CpMoMnPt(PPh(3))(2)(CO)(5)(μ(3)-Se)(2)，即化合物 5，以及 Cp(2)CoMoMn(CO)(5)(μ(3)-Se)(2)，即化合物 6。通过使用 Me(3)NO 在钼上进行脱羰反应，从化合物 6 得到含氧化合物 Cp(2)CoMo(O)Mn(CO)(5)(μ(3)-Se)(2)，即化合物 7。通过单晶 X 射线衍射分析确定了配合物 2 - 7 的分子结构。
