Electrochemistry of complexes of dichlorogermylene and dihalostannylenes with chromium, molybdenum, and tungsten pentacarbonyls

• Published in: Journal of organometallic chemistry 1999-02, Vol.574 (2), p.279-285
• Main Authors: Egorov, M.P., Basova, A.A., Gal’minas, A.M., Nefedov, O.M., Moiseeva, A.A., Rakhimov, R.D., Butin, K.P
• Format: Article
• Language: English
• Subjects: Complexes with chromium; Dihalogermylenes; Dihalostannylenes; Electrochemistry; Electronic structure; Mechanisms of reduction and oxidation; Molybdenum; Tungsten pentacarbonyls
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/S0022-328X(98)00906-1

Electrochemical behaviour of the transition metal complexes of dichlorogermylene and dihalostannylenes, (CO) 5MEX 2 · B (M=Cr, Mo, W; E=Ge, X=Cl; E=Sn, X=Cl, Br, I; B=THF, dioxane, DMF) has been studied in MeCN at 20°C. Both the reduction and the oxidation processes were found to be irreversible suggesting that the corresponding radical ions were unstable under these conditions; mechanisms of reduction and oxidation of (CO) 5MEX 2 · B were proposed. Electrochemical data obtained show that the electronic structures of (CO) 5MEX 2 · B complexes are similar to those of Fischer transition metal carbene complexes. Cyclic voltammetry data of (CO) 5MGeCl 2 · B (M=Cr, W; B=THF, dioxane, DMF) in DMF solutions clearly testify to the fact that the solvolytic cleavage of MGe bond in these complexes takes place leading to (CO) 5M · DMF and GeCl 2 · DMF species formation. The reduction of GeCl 2 · dioxane complex in DMF is discussed.