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

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.