Trinuclear [NiFe] Clusters as Structural Models for [NiFe] Hydrogenase Active Sites
Trinuclear [NiFe] Clusters as Structural Models for [NiFe] Hydrogenase Active Sites
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DOI：
10.1002/ejic.200400587
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发表时间：
2005
影响因子：
2.3
通讯作者：
D. Sellmann;Frank Lauderbach;F. Heinemann
中科院分区：
文献类型：
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作者：
D. Sellmann;Frank Lauderbach;F. Heinemann
(Fe (CH3COCH = CHPh) (CO) 3]反应与(Ni (4 ')) x (x = 1, 2)或者(Ni (' S 4 C 3我2 ')][' S 4 ' 2 - = 1,以叔(2-mercaptophenylthio)乙烷(2 -)的4 C 3我2的2 - = 1,二(2-mercaptophenylthio) 2, 2-dimethylpropane(2 -)]买得起三环的(镍铁)集群(Ni (4 ') {Fe (CO) 3} 2](1)和(Ni (' S 4 C 3我2 '){Fe (CO) 3} 2](2)和双核的铁我菲0复杂(Fe (CO) (' S 4 C 3我2 ')铁(CO) 3](3)。簇1和簇2的Ni- fe键长度与[NiFe]氢化酶的活性或还原态相似，是Ni和铁结合CO的硫主导配位球。因此，1和2可以作为[NiFe]氢化酶活性位点的结构模型配合物。‘ s4c3me2 ’配体与fecl2的结合。4h2o生成[Fe(‘ s4c3me2 ‘)] 2(4)，其双核表明’ s4c3me2 ’配体比其乙烯桥接衍生物柔韧性差，后者提供了先前报道的四聚体[Fe(' s4 ')] 4配合物。化合物4与2等量的CO反应生成[Fe(CO)('S 4 C 3 Me 2 ')] 2(5)，与4一样，它在所有常见的有机溶剂中只能少量溶解。配合物5即使以固态储存也容易失去CO。[Fe(ch3 COCH= CHPh)(CO) 3]与5反应生成唯一产物3。
[Fe(CH3COCH=CHPh)(CO)3] reacts with [Ni('S 4 ')] x (x = 1, 2) or [Ni('S 4 C 3 Me 2 ')] ['S 4 ' 2 - = 1,2-bis(2-mercaptophenylthio)-ethane(2-),'S 4 C 3 Me 2 ' 2 - = 1,3-bis(2-mercaptophenylthio)-2,2-dimethylpropane(2-)] to afford trinuclear [NiFe] clusters [Ni('S 4 '){Fe(CO) 3 } 2 ] (1) and [Ni('S 4 C 3 Me 2 '){Fe(CO) 3 } 2 ] (2) and the dinuclear Fe I I Fe 0 complex [Fe(CO)('S 4 C 3 Me 2 ')Fe(CO) 3 ] (3). Clusters 1 and 2 have Ni-Fe bond lengths similar to those of active or reduced states of [NiFe] hydrogenases, a sulfur-dominated coordination sphere of Ni and iron-bound CO. Therefore, 1 and 2 may serve as structural model complexes for the [NiFe] hydrogenase active site. Combination of the 'S 4 C 3 Me 2 ' ligand with FeCl 2 .4H 2 O yielded [Fe('S 4 C 3 Me 2 ')] 2 (4), the dinuclearity of which suggests that the 'S 4 C 3 Me 2 ' ligand is less flexible than its ethylene-bridged derivative, which affords a tetrameric [Fe('S 4 ')] 4 complex reported earlier. Compound 4 reacts with 2 equiv. of CO to give [Fe(CO)('S 4 C 3 Me 2 ')] 2 (5), which like 4 is only sparingly soluble in all common organic solvents. Complex 5 easily loses CO even if stored in the solid state. [Fe(CH 3 COCH= CHPh)(CO) 3 ] reacts with 5 to afford 3 as the onlv product.