Komplexchemischer Aufbau cyclischer 1,2-Dithiolato-Liganden mit dem nido-Cluster [(CO)3FeS]2. — Molekülstruktur und partielle S-Oxidation von Hexacarbonyl(μ2-cis-1,2-cyclohexandithiolato-S,S)dieisen

Komplexchemischer Aufbau cyclischer 1,2-Dithiolato-Liganden mit dem nido-Cluster [(CO)3FeS]2. — Molekülstruktur und partielle S-Oxidation von Hexacarbonyl(μ2-cis-1,2-cyclohexandithiolato-S,S)dieisen
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Aufbau cyclischer 1,2-Dithiolato-Liganden mit dem nido-Cluster [(CO)3FeS]2 — Molekülstruktur 和partielle S-Oxidation von Hexacarbonyl(μ2-cis-1,2-cyclohexandithiolato-S,S)dieisen。

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发表时间:
1990
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通讯作者:
H. Mayer
H. Mayer
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作者:
A. Kramer;Regine Lingnau;I. Lorenz;H. Mayer

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含巢簇[(CO)3,FeS]2的环状1,2-二硫醇配体的络合化学合成- 六羰基(μ2,-cis-1,2-环己烷二硫醇合-S,S)二铁的分子结构和部分S-氧化 通过光化学诱导的[2+2]环加成反应,将C6 H10、C8 C14、C5 H6、C8 C1, 2和C7 H8环烯、二烯和三烯插入到巢簇[(CO)3FeS]2(1)的S-S键中,得到配合物2-6;因此,饱和和不饱和的环状1,2-二硫杂环戊烯配体可以μ2-桥联方式选择性地构建到配合物上。X射线衍射分析表明,μ2- 1,2-环己烷二硫醇基-S,S配合物2a具有假四面体骨架[(CO)3FeS]2,空间群P21/c,S2部分由环己烷桥联,具有1,2-顺式构型.例如,进行2a的部分S氧化,通过将一个硫醇基选择性转化为亚磺酸基官能团而得到2b。
Complex-Chemical Synthesis of Cyclic 1.2-Dithiolato Ligands with the nido Cluster [(CO)3,FeS]2. — Molecular Structure and Partial S-Oxidation of Hexacarbonyl(μ2,-cis-1,2-cyclohexanedithiolato-S,S)diiron The cyclic alkenes, dienes, and trienes C6H10, C8C14, C5H6, C8C12 and C7H8 are inserted into the S-S bond of the nido cluster [(CO)3FeS]2 (1) by photochemically induced [2+2] cycloaddition reactions to give the complexes 2–6; thus, saturated and unsaturated cyclic 1,2-dithiolato ligands can be selectively built onto the complex in a μ2-bridging fashion. According to an X-ray structure analysis, the μ2-1,2-cyclohexanedithiolato-S,S complex 2a with the pseudotetrahedral skeleton [(CO)3FeS]2 crystallizes in the monoclinic space group P21/c; the S2 moiety is bridged by cyclohexane with 1,2-cis configuration. As an example, the partial S oxidation of 2a was carried out, leading to 2b by selective transformation of one thiolato into a sulfenato function.