Study of Redox-induced Reactions of Vinylidene and bis-Vinylidene Complexes of Manganese |
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Authors: | M. G. Peterleitner D. A. Valyaev L. N. Novikova O. V. Semeikin N. A. Ustynyuk |
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Affiliation: | (1) Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, GSP-1, 119813, Russia |
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Abstract: | Oxidative dehydrodimerization of some phenylvinylidene complexes of manganese is studied by cyclic voltammetry. In the case of (5-C5H5)(CO)2Mn=C=C(H)Ph, the process occurs as the homolysis of the C–H bond in the radical cation of {(5-C5H5)(CO)2Mn=C=C(H)Ph}+· and the dimerization of intermediate -phenylethinyl cation [(5-C5H5)(CO)2Mn–CC–Ph]+ to a binuclear dication of bis-carbine type (5-C5H5)(CO)2Mn+C– C(Ph)=C(Ph)–CMn+(CO)2(5-C5H5). The reduction of the latter leads to binuclear bis-vinylidene complex (5-C5H5)(CO)2Mn=C=C(Ph)–C(Ph)=C=Mn(CO)2(5-C5H5). Oxidative dehydrodimerization of complexes (5-C5R5)(CO)(L)Mn=C=C(H)Ph (R = H, L = PPh3; R = Me, L = CO) occurs through the immediate C–C coupling of radical cations {(5-C5R5)(CO)(L)Mn=C=C(H)Ph}+· and yields binuclear dication bis-carbine complexes (5-C5R5)(CO)(L)Mn+C–C(H)(Ph)–C(H)(Ph)–CMn+(CO)(L)(5-C5R5), whose reduction leads to neutral compounds (5-C5H5)(CO)2Mn=C=C(Ph)–C(Ph)=C=Mn(CO)(L)(5-C5H5). Complex (5-C5H5)(CO)2Mn=C=C(Ph)–C(Ph)=C=Mn(CO)2(5-C5H5) undergoes the oxidation-induced nucleophilic addition of water, forming cyclic bis-carbene product with a bridge heterocyclic ligand (-3,4-diphenyl-2,5-dihydro-2,5-diylidene)-bis-(5-cyclopentadienyldicarbonyl manganese). |
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Keywords: | vinylidene complexes cyclic voltammetry oxidative dehydrodimerization nucleophilic addition |
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