Dinitrosyl iron complexes relevant to Rieske cluster nitrosylation.

Dinitrosyl iron complexes relevant to Rieske cluster nitrosylation.
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DOI:
10.1021/ja9030159
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发表时间:
2009-06-17
影响因子:
15
通讯作者:
Lippard, Stephen J.
Lippard, Stephen J.
中科院分区:
化学1区
文献类型:
--
作者:
Tonzetich, Zachary J.;Do, Loi H.;Lippard, Stephen J.

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Rieske簇模型配合物(Et4N)2[(N2CHPh)Fe2S2(s2 -o-羟基)](N2CHPh = 2,2 ' -(苯基亚甲基)双(3-甲基吲哚)二离子)的反应s2 -o-羟基= 1,2-苯基二甲基硫醇的二离子)与一氧化氮的反应导致铁-硫核的分解并形成{Fe(NO)2}9二硝基硅基配合物。这些dics(包括新化合物(Et4N)[(N2CHPh)Fe(NO)2])的分离和表征表明,在涉及NO的反应中,合成的Riekse簇与纯硫酸盐结合的Fe2S2簇具有同源性。为了模拟Rieske簇衍生二硝基硅氧烷的富氮环境,制备了一种含有β-二酮酸配体的新型中性{Fe(NO)2}9 DNIC。该化合物的单电子还原得到可分离的{Fe(NO)2}10 DNIC。这些化合物是结构类似DNIC氧化还原伙伴的罕见例子。
Reaction of the Rieske cluster model complex (Et4N)2[(N2CHPh)Fe2S2(S2-o-xyl)] (N2CHPh = dianion of 2,2′-(phenylmethylene)bis(3-methylindole); S2-o-xyl = dianion of 1,2-phenylenedimethanethiol) with nitric oxide results in disassembly of the iron-sulfur core and formation of {Fe(NO)2}9 dinitrosyliron complexes. Isolation and characterization of these DNICs, including the new compound, (Et4N)[(N2CHPh)Fe(NO)2], demonstrates a homology between the synthetic Riekse cluster and purely thiolate bound Fe2S2 clusters in reactions involving NO. To model the nitrogen rich environment of Rieske cluster-derived dinitroysliron species, a new type of neutral {Fe(NO)2}9 DNIC was prepared containing a β-diketiminate ligand. One-electron reduction of this compound affords the isolable {Fe(NO)2}10 DNIC. These compounds represent a rare example of structurally analogous DNIC redox partners.
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