Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, the Netherlands.
Dalton Trans. 2017 Oct 10;46(39):13590-13596. doi: 10.1039/c7dt02631e.
The two heterodinuclear nickel-ruthenium complexes [Ni(xbSmS)RuCp(PPh)]PF and [Ni(xbSmSe)RuCp(PPh)]PF (HxbSmS = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene, HxbSmSe = 1,2,-bis(2-thiabutyl-3,3-dimethyl-4-selenol)benzene, Cp = cyclopentadienyl) were synthesized as biomimetic models of [NiFe] and [NiFeSe] hydrogenases. The X-ray structural analyses of the complexes show that the two NiRu complexes are isomorphous; in both NiRu complexes the nickel(ii) centers are coordinated in a square-planar environment with two thioether donor atoms and two thiolate or selenolate donors that are bridging to the ruthenium(ii) center. The Ru(ii) ion is further coordinated to a η-cyclopentadienyl group and a triphenylphosphane ligand. These complexes catalyze hydrogen evolution in the presence of acetic acid in acetonitrile solution at around -2.20 V vs. Fc/Fc with overpotentials of 810 and 830 mV, thus they can be regarded as functional models of the [NiFe] and [NiFeSe] hydrogenases.
两个异双核镍-钌配合物[Ni(xbSmS)RuCp(PPh)]PF 和 [Ni(xbSmSe)RuCp(PPh)]PF（HxbSmS = 1,2-双(4-巯基-3,3-二甲基-2-噻丁基)苯，HxbSmSe = 1,2,-双(2-噻丁基-3,3-二甲基-4-硒醇)苯，Cp = 环戊二烯基）被合成作为 [NiFe] 和 [NiFeSe] 氢化酶的仿生模型。配合物的 X 射线结构分析表明，两个 NiRu 配合物是同构的；在两个 NiRu 配合物中，镍（ii）中心以平面正方形环境配位，有两个硫醚供体原子和两个桥接到钌（ii）中心的硫醇或硒醇供体。Ru(ii)离子进一步与一个 η-环戊二烯基和一个三苯基膦配体配位。这些配合物在乙腈溶液中存在乙酸的情况下在约-2.20 V vs. Fc/Fc 下催化氢气的产生，过电势为 810 和 830 mV，因此它们可以被视为 [NiFe] 和 [NiFeSe] 氢化酶的功能模型。
