Сибирский федеральный университет

Тип публикации: статья из журнала

Год издания: 2017

Идентификатор DOI: 10.1016/j.ica.2017.04.004

Аннотация: Redox-induced transformations of bi-Cp(CO)2RePd(?-C[dbnd]CHPh)(PPh3)2 (2), Cp(CO)2RePd(?-C[dbnd]CHPh)(P-P) [P-P = ?2-Ph2P(CH2)2PPh2 (dppe) (3), ?2-Ph2P(CH2)3PPh2 (dppp) (4)], Cp(CO)2ReFe(?-C[dbnd]CHPh)(CO)4 (5) and trinuclear Cp(CO)2ReFe2(?3-C[dbnd]CHPh)(CO)6 (6), CpReFePd(µ3-C[dbnd]CHPh)(CO)5(P-P) [P-P = dppe (7), dppp (8)] heterometallic vinylidene complexes derived from Cp(CO)2Re[dbnd]C[dbnd]CHPh (1) were investigated by electrochemical methods. The oxidation processes of clusters 7 and 8 were studied by EPR spectroscopy. The electrochemical properties of clusters 7 and 8 were shown to depend on the nature of the chelate diphosphine ligand at the palladium center in contrast to complexes 3 and 4. The oxidation of complexes 2–4 was found to result in the Re-Pd, Pd-C bond cleavage and formation of rhenium complex 1 and Pd-containing fragments. The oxidation of 7 and 8 resulted in the formation of the radical cations 7+[rad] and 8+[rad], which sequentially transformed into a number of intermediate products: Cp(CO)2RePd(?-C[dbnd]CHPh)(P-P), [Fe(CO)3]+[rad], [CpReFe2(µ3-C[dbnd]CHPh)(CO)6]+[rad] and others. The final products of their oxidation in both cases were triangular clusters (CO)8Fe2Pd(P-P) [P-P = dppe (9), dppp (10)] and rhenium complex 1. The molecular structure of cluster 7 was established by X-ray diffraction analysis. © 2017 Elsevier B.V.

Журнал: Inorganica Chimica Acta

Выпуск журнала: Vol. 463

Номера страниц: 70-79

• Burmakina Galina V. (RAS, Krasnoyarsk Sci Ctr, Fed Res Ctr, Inst Chem & Chem Technol,SB, Akademgorodok 50-24, Krasnoyarsk 660036, Russia; Siberian Fed Univ, Svobodny Prospect 79, Krasnoyarsk 660041, Russia)
• Verpekin Victor V. (RAS, Krasnoyarsk Sci Ctr, Fed Res Ctr, Inst Chem & Chem Technol,SB, Akademgorodok 50-24, Krasnoyarsk 660036, Russia)
• Maksimov Nikolai G. (RAS, Krasnoyarsk Sci Ctr, Fed Res Ctr, Inst Chem & Chem Technol,SB, Akademgorodok 50-24, Krasnoyarsk 660036, Russia; RAS, Krasnoyarsk Sci Ctr, Fed Res Ctr, SB, Akademgorodok 50, Krasnoyarsk 660036, Russia)
• Zimonin Dmitry V. (RAS, Krasnoyarsk Sci Ctr, Fed Res Ctr, Inst Chem & Chem Technol,SB, Akademgorodok 50-24, Krasnoyarsk 660036, Russia)
• Piryazev Dmitry A. (Russian Acad Sci, Nikolaev Inst Inorgan Chem, Siberian Branch, Acad Lavrentiev Ave 3, Novosibirsk 630090, Russia)
• Chudin Oleg S. (RAS, Krasnoyarsk Sci Ctr, Fed Res Ctr, Inst Chem & Chem Technol,SB, Akademgorodok 50-24, Krasnoyarsk 660036, Russia)
• Rubaylo Anatoly I. (RAS, Krasnoyarsk Sci Ctr, Fed Res Ctr, Inst Chem & Chem Technol,SB, Akademgorodok 50-24, Krasnoyarsk 660036, Russia; Siberian Fed Univ, Svobodny Prospect 79, Krasnoyarsk 660041, Russia; RAS, Krasnoyarsk Sci Ctr, Fed Res Ctr, SB, Akademgorodok 50, Krasnoyarsk 660036, Russia)

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