Reactions of 1,2,4‐Trithiolane, 1,2,5‐Trithiepane, 1,2,5‐Trithiocane and 1,2,6‐Trithionane with Nonacarbonyldiiron: Structural Determination and Electrochemical Investigation

The reactions of 1,2,4‐trithiolane ( 1 ), 1,2,5‐trithiepane ( 6 ), 1,2,5‐trithiocane ( 12 ) and 1,2,6‐trithionane ( 10 ) with nonacarbonyldiiron ( 2 ) have been investigated. A novel diiron model complex, which can serve as a model complex of the active site of [Fe‐only]‐hydrogenase, was formed from the reaction with 1 . In contrast, the reaction of 6 with 2 afforded the trinuclear iron cluster 7 . Interestingly, the diiron compound 11 was obtained with 1,2,6‐trithionane ( 10 ), which can be attributed to the more flexible dithiolato ligand 10 . Furthermore, the reaction with 1,2,5‐trithiocane ( 12 ) yielded the trinuclear cluster 13 . X‐ray structure analyses were performed on compounds 3 , 7 , 10 , 11 and 13 . The reactions of the reduced iron species 3 with pivalic acid (HP) were studied electrochemically. The most significant features of the experimental cyclic voltammograms (CVs) could be reproduced by digital simulation on the basis of a reaction scheme that includes both the coordination of HP as well as the catalytic generation of hydrogen. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)