Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, USA.
J Am Chem Soc. 2010 Mar 24;132(11):3691-3. doi: 10.1021/ja100214e.
The first phosphinidene complexes of scandium are reported in this contribution. When complex (PNP)Sc(CH(3))Br (1) is treated with 1 equiv of LiPH[Trip] (Trip = 2,4,6-(i)Pr(3)C(6)H(2)), the dinuclear scandium phosphinidene complex (PNP)Sc(mu(2)-P[Trip]) (2) is obtained. However, treating 1 with a bulkier primary phosphide produces the mononuclear scandium ate complex [(PNP)Sc(mu(2)-P[DMP])(mu(2)-Br)Li] (3) (DMP = 2,6-Mes(2)C(6)H(3)). The Li cation in 3 can be partially encapsulated with DME to furnish a phosphinidene salt derivative, (PNP)Sc(mu(2)-P[DMP])(mu(2)-Br)Li(DME)] (4). We also demonstrate that complex 3 can readily deliver the phosphinidene ligand to organic substrates such as OCPh(2) and Cl(2)PMes* as well as inorganic fragments such as Cp(2)ZrCl(2), Cp*(2)TiCl(2), and Cp(2)TiCl(2) in the presence of P(CH(3))(3). Complexes 2-4 have been fully characterized, including single crystal X-ray diffraction and DFT studies.
本文报道了首例钪的膦烯配合物。当配合物(PNP)Sc(CH(3))Br（1）与 1 当量的 LiPH[Trip]（Trip = 2,4,6-(i)Pr(3)C(6)H(2)）反应时，得到双核钪膦烯配合物(PNP)Sc(mu(2)-P[Trip])（2）。然而，用较大的伯膦化物处理 1 得到单核钪烷基金属配合物[(PNP)Sc(mu(2)-P[DMP])(mu(2)-Br)Li]（3）（DMP = 2,6-Mes(2)C(6)H(3)）。3 中的锂离子可以部分被 DME 包裹，得到膦烯盐衍生物(PNP)Sc(mu(2)-P[DMP])(mu(2)-Br)Li(DME)]（4）。我们还证明，配合物 3 可以在 P(CH(3))(3)存在下，很容易将膦烯配体传递给有机底物如 OCPh(2)和 Cl(2)PMes以及无机片段如 Cp(2)ZrCl(2)、Cp(2)TiCl(2)和 Cp(2)TiCl(2)。2-4 配合物已被全面表征，包括单晶 X 射线衍射和 DFT 研究。
