Towards Reagents for Bimetallic Activation Reactions: Polyhydride Complexes with Ru2H3, Ru2ZnH6, and Cu2Ru2H6 Cores
Towards Reagents for Bimetallic Activation Reactions: Polyhydride Complexes with Ru2H3, Ru2ZnH6, and Cu2Ru2H6 Cores
复制标题
用于双金属活化反应的试剂：具有 Ru2H3、Ru2ZnH6 和 Cu2Ru2H6 核的多氢化物配合物
DOI：
10.1002/ejic.201300233
复制
发表时间：
2013
影响因子：
2.3
通讯作者：
S. Grimme
中科院分区：
文献类型：
--
作者：
Markus Plois;R. Wolf;Waldemar Hujo;S. Grimme
本文研究了fac-[RuH_3（PR_3）_3]-阴离子（R = Ph，C_6 H_4 ~（-4）-Me）在制备新型低聚过渡金属杂多酸盐中的应用。锂盐[Li（thf）x{Ru（μ-H）3（PPh 3）3}] {1：R = Ph，x = 3; 1′：R = C6 H4 -4-Me（Tol），x = 2.5}与[Cp*RuCl]4（Cp* = C5 Me 5）、ZnCl 2和CuCl（SMe 2）反应生成新的寡聚多嵌段配合物。合成了配合物[Cp*Ru（μ-H）3 Ru（PR 3）3]（2：R = Ph，2′：R = Tol），[Zn{Ru（μ-H）3（PPh 3）3}2]（3）和[Cu 2 {Ru（μ-H）3（PPh 3）3}2]（4），并用多核NMR，IR和微量分析进行了表征.通过X射线晶体学确定了分子结构。在PBE-D3/def 2-TZVP水平上的密度泛函理论计算支持新的多氢化物配合物的结构。讨论了分子内伦敦色散相互作用对优化几何构型的影响。
The utility of the fac-[RuH3(PR3)3]– anion (R = Ph, C6H4-4-Me) for the preparation of new oligonuclear transition metal polyhydrides has been examined. The lithium salts [Li(thf)x{Ru(μ-H)3(PPh3)3}] {1: R = Ph, x = 3; 1′: R = C6H4-4-Me (Tol), x = 2.5} react with [Cp*RuCl]4 (Cp* = C5Me5), ZnCl2, and CuCl(SMe2) to form new oligonuclear polyhydrido complexes. The compounds [Cp*Ru(μ-H)3Ru(PR3)3] (2: R = Ph, 2′: R = Tol), [Zn{Ru(μ-H)3(PPh3)3}2] (3), and [Cu2{Ru(μ-H)3(PPh3)3}2] (4) were synthesized and characterized by multinuclear NMR and IR spectroscopy, and microanalysis. The molecular structures were determined by X-ray crystallography. Density functional theory calculations at the PBE-D3/def2-TZVP level support the proposed structures of the new polyhydride complexes. The impact of intramolecular London dispersion interactions on the optimized geometries is discussed.