一个含有二氢-二(N-甲基-2-巯基咪唑)硼酸盐配体的钌-苯肼阳离子配合物的合成、晶体结构与密度泛函理论计算(英文)

Synthesis, Crystal Structure and Density Functional Calculation of a Cationic Ruthenium-phenylhydraizine Complex with Dihydridobis(N-methyl-2-mercaptoimidazolyl) borate Ligand

以四氢呋喃(THF)作溶剂,将[Ru(PPh3)3Cl2]与等摩尔的K[H2B(timMe)2]和过量的苯肼(PhNHNH2)反应,得到1个阳离子配合物[Ru(PPh3){κ3-H,S,S’-H2B(timMe)2}(PhNHNH2)2]Cl·0.5CH2Cl2(1)。单晶X-射线衍射分析显示,配合物1中的中心钌原子与三齿螯合配体[H2B(timMe)2](κ3-H,S,S’)、1个三苯基膦(PPh3)、2个顺式cisPhNHNH2配位形成1个八面体几何构型。通过密度泛函理论计算的价键分析,可确定配合物1中HOMO和LUMO间的能隙较窄,只有3.62 eV。

Treatment of [Ru（PPh3）3Cl2] with the same equiv.of K[H2B（timMe）2] in tetrahydrofuran （THF） in the presence of excess PhNHNH2 afforded the cationic complex [Ru（PPh3）{κ3-H,S,S＇-H2B（timMe）2}-（PhNHNH2）2]Cl·0.5CH2Cl2 （1）.X-ray analysis of the single crystal shows that the geometry at ruthenium in 1 is pseudo-octahedral,given the constraints of one tris-chelated [H2B（timMe）2]-ligand in a κ3-H,S,S＇ mode,one PPh3 ligand and two mutually cis PhNHNH2 moieties.Valence bond analysis of density functional theory calculations identifies the energy gap between HOMO and LUMO in 1 is narrow with the value of 3.62 eV.