pH-dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases
pH-dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases
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DOI：
10.1039/b807555g
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发表时间：
2008-01-01
影响因子：
4
通讯作者：
Ogo, Seiji
中科院分区：
文献类型：
--
作者：
Kure, Bunsho;Matsumoto, Takahiro;Ogo, Seiji
以水溶性双（多硫酸盐）（多氢化物）NiRu配合物Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N，N'-二甲基-N，N'-双（2-巯基乙基）-1,3-丙二胺}作为[NiFe]加氢酶的功能模型，研究了气态同位素与介质同位素之间ph依赖的氢同位素交换反应和羰基化合物的加氢反应。在酸性介质中（pH 4 ~ 6）， Ni(II)(mu-SR)(2)(mu-H)Ru（II）配合物的mu-H配体具有H+性质，配合物催化气态同位素与介质同位素之间的氢同位素交换反应。提出了气态同位素与介质同位素通过低价Ni(I)(mu-SR)(2)Ru(I)配合物进行氢同位素交换反应的机理。相反，在中性碱性介质中（pH 7-10）， Ni(II)(mu-SR)(2)(mu-H)Ru（II）配合物的mu-H配体充当H(-)，配合物催化羰基化合物的加氢。
The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H+ properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds.