School of Chemistry, Bharathidasan University, Tiruchirappalli 620024, Tamil Nadu, India.
Spectrochim Acta A Mol Biomol Spectrosc. 2010 Feb;75(2):713-8. doi: 10.1016/j.saa.2009.11.044. Epub 2009 Nov 24.
Mononuclear ruthenium(III) complexes of the type [RuX(EPh(3))(2)(L)] (E=P or As; X=Cl or Br; L=dibasic terdentate dehydroacetic acid thiosemicarbazones) have been synthesized from the reaction of thiosemicarbazone ligands with ruthenium(III) precursors, [RuX(3)(EPh(3))(3)] (where E=P, X=Cl; E=As, X=Cl or Br) and [RuBr(3)(PPh(3))(2)(CH(3)OH)] in benzene. The compositions of the complexes have been established by elemental analysis, magnetic susceptibility measurement, FT-IR, UV-vis and EPR spectral data. These complexes are paramagnetic and show intense d-d and charge transfer transitions in dichloromethane. The complexes show rhombic EPR spectra at LNT which are typical of low-spin distorted octahedral ruthenium(III) species. All the complexes are redox active and display an irreversible metal centered redox processes. Complex [RuCl(PPh(3))(2)(DHA-PTSC)] (5) was used as catalyst for transfer hydrogenation of ketones in the presence of isopropanol/KOH and was found to be the active species.
单核钌(III)配合物的类型 [RuX(EPh(3))(2)(L)]（E=P 或 As；X=Cl 或 Br；L=二羧酸三齿去氢乙酸缩氨硫脲）已通过反应合成从硫代缩氨硫脲配体与钌(III)前体，[RuX(3)(EPh(3))(3)]（其中 E=P，X=Cl；E=As，X=Cl 或 Br）和[RuBr(3)(PPh(3))(2)(CH(3)OH)]在苯中。通过元素分析、磁化率测量、FT-IR、UV-vis 和 EPR 光谱数据确定了配合物的组成。这些配合物是顺磁性的，并在二氯甲烷中显示出强烈的 d-d 和电荷转移跃迁。这些配合物在 LNT 下显示出菱形 EPR 光谱，这是低自旋扭曲八面体钌(III)物种的典型特征。所有配合物都是氧化还原活性的，并显示不可逆的金属中心氧化还原过程。配合物[RuCl(PPh(3))(2)(DHA-PTSC)]（5）在异丙醇/KOH 的存在下被用作酮的转移氢化催化剂，并被发现是活性物质。
