Oleg V. Semeikin

Oxidative dehydrodimerization of manganese phenylvinylidene complex (η5-C5H5)(CO)2MnCC(H)Ph. X-ray structure of phenyl(trityl)vinylidene complex (η5-C5H5)(CO)2MnCC(CPh3)Ph

Abstract The oxidatively induced dehydrodimerization of the manganese vinylidene complex (η 5 -C 5 H 5 )(CO) 2 MnCC(H)Ph ( I ) to the bis-vinylidene compound (η 5 -C 5 H 5 )(CO) 2 MnCC(Ph)C(Ph)CMn(CO) 2 (η 5 -C 5 H 5 ) ( II ) proceeds via C β H bond homolysis in the radical cation ( I + ) and is thought to involve the formally 16-electron mononuclear σ-phenylethynyl cation [(η 5 -C 5 H 5 )(CO) 2 MnCCPh] + ( III ) and the bis-carbyne dication [(η 5 -C 5 H 5 )(CO) 2 MnCC(Ph)C(Ph)CMn(CO) 2 (η 5 -C 5 H 5 )] 2+ ( II 2+ ) as the key sequential intermediates. Compound II 2+ was characterized by IR and CV. The reduction of II 2+ with (C 6 H 6 ) 2 Cr gave II in an 80% yield. Compound II can be prepared more conveniently by treating I with (C 5 H 5 ) 2 FeBF 4 in the presence of Et 3 N. The interaction of I with Ph 3 CPF 6 yields the trityl(phenyl)vinylidene complex (η 5 -C 5 H 5 )(CO) 2 MnCC(CPh 3 )Ph ( IV ) as a result of the electrophilic attack of the trityl cation on C β followed by the loss of a proton. The structure of IV was established by an X-ray structural analysis.

Electrochemical Study of a Heterobinuclear pyridylvinylidene Complex Cp(CO)2Fe [μ-C=CH(2-C5H4N)]PdI

Victor V. Verpekin*a, Galina V. Burmakinaa,b, Dmitry V. Zimonina, Nina I. Pavlenkoa, Oleg. V. Semeikinc and Arkadii Z. Kreindlinc aInstitute of Chemistry and Chemical Technology SB RAS FRC “Krasnoyarsk Science Center SB RAS” 50/24 Akademgorodok, Krasnoyarsk, 660036, Russia bSiberian Federal University 79 Svobodny, Krasnoyarsk, 660041, Russia cA.N. Nesmeyanov Institute of Organoelement Compounds RAS 28 Vavilova Str., Moscow, 119991, Russia

Crystal structure of μ-carbonyl-1:2κ2C:C-carbonyl-1κC-(1η5-cyclo­penta­dien­yl)iodido-2κI-[μ-2-(pyridin-2-yl)ethene-1,1-diyl-1κC1:2κ2N,C1]ironpalladium(Fe—Pd) benzene monosolvate

The title binuclear μ-pyridylvinylidene FePd complex (FePd1) was obtained from Cp(CO)2FeI and 2-ethynylpyridine in diisorpopylamine in the presence of PdCl2