Synthesis, structural characterization and conversion of dinuclear iron-sulfur clusters containing the disulfide ligand: [CpFe(mu-eta(2):eta(2)-bdt)(cis-mu-eta(1):eta(1)-S-2)FeCp], [CpFe(mu-S(C6H4S2))(cis-mu-eta(1):eta(1)-S-2)FeCp], and [{CpFe(bdt)}(2)(tr
Synthesis, structural characterization and conversion of dinuclear iron-sulfur clusters containing the disulfide ligand: [CpFe(mu-eta(2):eta(2)-bdt)(cis-mu-eta(1):eta(1)-S-2)FeCp], [CpFe(mu-S(C6H4S2))(cis-mu-eta(1):eta(1)-S-2)FeCp], and [{CpFe(bdt)}(2)(tr
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含有二硫配体的双核铁硫簇的合成、结构表征和转化：[CpFe(mu-eta(2):eta(2)-bdt)(cis-mu-eta(1):eta(1)-S
DOI：
10.1039/c7dt00450h
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发表时间：
2017
影响因子：
4
通讯作者：
Qu Jingping
中科院分区：
文献类型：
--
作者：
Ji Xiaoxiao;Tong Peng;Yang Dawei;Wang Baomin;Zhao Jinfeng;Li Yang;Qu Jingping
[Cp*Fe(μ-η2：η4-bdt)FeCp*](1，Cp*=η5-C5Me5，Bdt=苯-1，2-二硫代苯)与1/4当量。元素硫(S8)合成了一个含顺-1，2-二硫配体的双核铁硫簇合物[Cp*Fe(μ-η2：η2-bdt)(cis-μ-η1：η1-S2)FeCp*](2)。当络合物2进一步与1/8当量相互作用时。在S8中，另一个硫原子插入Fe-S键得到稀有产物[Cp*Fe(μ-S(C6H4S2))(cis-μ-η1：η1-S2)FeCp*](3)。意外地，从配合物1与1/2当量的反应中分离到了一个反式-1，2-二硫键桥联二铁配合物[{Cp*Fe(Bdt)}2(Trans-μ-η1：η1-S2)](4)。S8，它代表[2Fe-2S]铁氧还蛋白类型簇合物的结构异构体。此外，顺式-1，2-二硫键桥联配合物3在室温下可以通过自组装反应缓慢地转变为反式-1，2-二硫键桥联配合物4和[Cp*Fe(μ-η2：η2-S2)(cis-μ-η1：η1-S2)FeCp*](5)。
The treatment of [Cp*Fe(μ–η2:η4-bdt)FeCp*] (1, Cp* = η5-C5Me5, bdt = benzene-1,2-dithiolate) with 1/4 equiv. of elemental sulfur (S8) gave a dinuclear iron–sulfur cluster [Cp*Fe(μ–η2:η2-bdt)(cis-μ–η1:η1-S2)FeCp*] (2), which contains a cis-1,2-disulfide ligand. When complex 2 further interacted with 1/8 equiv. of S8, another sulfur atom inserted into an Fe–S bond to give a rare product [Cp*Fe(μ-S(C6H4S2))(cis-μ–η1:η1-S2)FeCp*] (3). Unexpectedly, a trans-1,2 disulfide-bridged diiron complex [{Cp*Fe(bdt)}2(trans-μ–η1:η1-S2)] (4) was isolated from the reaction of complex 1 with 1/2 equiv. of S8, which represents a structural isomer of [2Fe–2S] ferredoxin-type clusters. In addition, cis-1,2-disulfide-bridged complex 3 can slowly convert into trans-1,2-disulfide-bridged complex 4 and the complex [Cp*Fe(μ–η2:η2-S2)(cis-μ–η1:η1-S2)FeCp*] (5) by self-assembly reaction at ambient temperature, which is evidenced by time-dependent 1H NMR spectroscopy.