Komplexchemischer Aufbau cyclischer 1,2‐Dithiolato‐Liganden mit dem nido ‐Cluster [(CO) 3 FeS] 2 . — Molekülstruktur und partielle S ‐Oxidation von Hexacarbonyl(μ 2 ‐ 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(μ 2 ,‐ cis ‐1,2‐cyclohexanedithiolato‐S,S)diiron The cyclic alkenes, dienes, and trienes C 6 H 10 , C 8 C 14 , C 5 H 6 , C 8 C 12 and C 7 H 8 are inserted into the S‐S bond of the nido cluster [(CO) 3 FeS] 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 μ 2 ‐bridging fashion. According to an X‐ray structure analysis, the μ 2 ‐1,2‐cyclohexanedithiolato‐ S,S complex 2a with the pseudotetrahedral skeleton [(CO) 3 FeS] 2 crystallizes in the monoclinic space group P 2 1 /c; the S 2 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.