Schneider, Jorg J.; Hagen, Jorg; Spickermann, Dirk; Blaser, Dieter; Boese, Roland; De Biani, Fabrizia F.; Laschi, Franco; Zanello, Piero:

Synthesis, structure, and spectroelectrochemical investigation of novel ternary Co/S(Se)/Sn clusters derived from binary cobalt stannanediyl complexes.

In: Chemistry--A European Journal, Jg. 6 (2000) ; Nr. 2, S. 237-246
ISSN: 0947-6539
Zeitschriftenaufsatz / Fach: Chemie
The synthesis and structure of heterobimetallic Co/Sn complexes [(h5-CpR)Co(Sn{CH(SiMe3)2}2)(h2-C2H4)] (CpR = C5Me5 2; C5EtMe4 3) are described. Insertion reactions of S and Se into the unbridged heteronuclear Co-Sn bonds of [(h5-Cp)Co(Sn{CH(SiMe3)2}2)(h2-C2H4)], 2, and 3 were studied. Depending on the stoichiometry of the chalcogen element used, novel ternary Sn-chalcogen-Co clusters ([(h5-C5Me4R)Co(m-S)2(Sn{CH(SiMe3)2}2)] (8, R = Me; R = Et), 9 (shown as I; R1 = C5Me5), 15 (Cp/Se analog of 9), and 16 (Se analog of 9)) can be synthesized, and their mol. structures, which represent rare examples of crystallog. characterized cases of ternary transition metal/chalcogen/Sn complexes, were detd. Electrochem. shows that complexes 8 and 9 are able to support reversibly either the removal or addn. of one electron. Insertion of a further (Cp)Co-E (E = chalcogen) fragment significantly affects the electron distribution and causes complexes 9 and 16 to undergo two consecutive 1-electron oxidns. The EPR spectra of the resp. monocations were recorded. In all cases, the unpaired electron strongly interacts with the Co nucleus(i), thus testifying that the main contribution to the relevant HOMO orbitals comes from the Co atom(s).