Rosenkoetter Kyle E, Ziller Joseph W, Heyduk Alan F
Department of Chemistry, University of California, Irvine, California 92617, USA.
Dalton Trans. 2017 May 2;46(17):5503-5507. doi: 10.1039/c6dt04451d.
Complexes of the general formula W[SNS]M(dppe) (M = Pd, Pt; [SNS]H = bis(2-mercapto-p-tolyl)amine; dppe = 1,2-bis(diphenylphosphino)ethane) were prepared by combining the corresponding (dppe)MCl synthon with W[SNS] under reducing conditions. X-ray diffraction studies revealed the formation of a heterobimetallic complex supported by a single thiolate bridging ligand and a short metal-metal bond between the tungsten and palladium or platinum. Electrochemical and computational results show that the frontier orbitals lie predominantly on the W[SNS] fragment suggesting that it behaves as a redox-active metalloligand in these complexes.
通式为W[SNS]M(dppe)(M = Pd、Pt;[SNS]H = 双(2-巯基对甲苯基)胺;dppe = 1,2-双(二苯基膦基)乙烷)的配合物是通过在还原条件下将相应的(dppe)MCl合成子与W[SNS]结合制备的。X射线衍射研究表明,形成了一种由单个硫醇盐桥连配体支撑的异双金属配合物,并且钨与钯或铂之间存在短的金属-金属键。电化学和计算结果表明,前沿轨道主要位于W[SNS]片段上,这表明它在这些配合物中表现为氧化还原活性金属配体。