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

Abstract

The cyclic alkenes, dienes, and trienes C6HI0, C8Cl4, C,H6, hexanedithiolato-S,S complex 2 a with the pseudotetrahedral CSCl2, and C7H8 are inserted into the S-S bond of the nido skeleton [(CO),FeSIz crystallizes in the monoclinic space cluster [(C0),FeSIz (1) by photochemically induced [2+2] cy-group P21/c; the Sz moiety is bridged by cyclohexane with cloaddition reactions to give the complexes 2-6; thus, satu-1,Zci.s configuration. As an example, the partial S oxidation rated and unsaturated cyclic 1,2-dithiolato ligands can be of 2 a was carried out, leading to 2b by selective transformation selectively built onto the complex in a p2-bridging fashion. of one thiolato into a sulfenato function.According to an X-ray structure analysis, the p2-1,2-cycloIn zusammenfassenden Arbeiten ist uber die besondere Reaktivitit des nido-Clusters [(CO)3FeS]2 (I) mehrfach berichtet worden'-3); 1 kann unter Erhaltung des Polyedergrusts Substitut i o n~-~~ und Reduktionsreaktionen ' ) sowie Insertionsreaktionen von koordinativ ungesattigten Verbindungen in die Fe -Fe-2%6) und S-S-Bindung'r3) eingehen. 1 kann aber auch durch reaktive M -M-Bindungen symmetrisch gespalten und zum gezielten Clusteraufbau herangezogen werden ' -I 1 ) .In diesem Zusammenhang haben vor allem Seyferth et al. auf die auffallende Ahnlichkeit des metallorganischen Disulfids 1 mit organischen Disulfiden hingewiesen I). MO-Berechnungen zufolge besitzt 1 als HOMO ein n(S -SYb-Orbital ' *I, was die besondere Reaktivitat der S -S-Bindung gegenuber Reduktionsmitteln ') und starken Nucleophilen Resultate und DiskussionBei der photochemischen Reaktion von [(CO)3FeS]2 (1) mit Cyclohexen bzw. Cycloocten gemaB G1. (1) und (2)

Revisiting the photochemical synthesis of [FeFe]-hydrogenase mimics: reaction optimization, mechanistic study and electrochemical behaviour

“…Similar low yields were obtained with both, acyclic 6 and cyclic 7 dienes. The only exceptions are ethylene 8 and p-benzoquinone, 9 that produce the corresponding photoadducts in 65% and 53% yields, respectively.…”

Platinum Complexes of Naphthalene‐1,8‐dichalcogen and Related Polyaromatic Hydrocarbon Ligands

“…[21] Thiolato±sulfenato (-SÀMÀS(=O)-) complexes have also been prepared through the mono-oxidation of dithiolate complexes of which the diiron compounds [{(OC) 3 -Fe} 2 SCH 2 CH 2 S(=O)] and [{(OC) 3 Fe} 2 SC 6 H 10 S(=O)] containing bridging 1,2-ethanesulfenatothiolato and 1,2-cyclohexylsulfenatothiolato ligands are illustrative examples. [22,23] This preparative method has also been utilised by Darensbourg and co-workers in the preparation a series of thiolato±sulfenato, disulfenato, thiolato±sulfinato, sulfenato±sulfinato and disulfinato complexes of nickel(ii) and palladium(ii) from bis(2-mercaptoethyl)-1,5-diazacyclooctane-M II (M = Ni, Pd) and N,N'-bis(2-methyl-2-mercaptopropyl)-1,5-diazacyclooctane-Ni II . [24±28] Some further examples of thiolato±sulfenato, thiolato±sulfinato and disulfinato complexes formed by oxidation of thiolate complexes are known.…”

Rational Synthesis of the Carbonyl(perthiolato)diiron [Fe2(S3CPh2)(CO)6] and Related Complexes

“…To test the generality of the new reaction, we also investigated the photoaddition of Fe 2 (S 2 )(CO) 5 (PPh 3 ) [8c] to thiobenzophenone. This reaction proceeded as above to give the adduct Fe 2 (S 3 CPh 2 )(CO) 5 (PPh 3 ) ( 2 ) in 45 % isolated yield.…”

“…[7] The reaction has been extended to other alkenes. [8] These photoadditions probably proceed via the diferrous sulfide Fe 2 (S) 2 (CO) 6 , an excited state of Fe 2 (S 2 )(CO) 6 . [9] …”