Study of Redox-induced Reactions of Vinylidene and bis-Vinylidene Complexes of Manganeseстатья
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 24 марта 2017 г.
Аннотация:Oxidative dehydrodimerization of some phenylvinylidene complexes of manganese is studied by cyclic voltammetry. In the case of (eta(5)-C5H5 )(CO)(2)Mn=C=C(H)Ph, the process occurs as the homolysis of the C-beta-H bond in the radical cation of {(eta(5) -C5H5)(CO)(2)Mn=C=(H)Ph}(+.) and the dimerization of intermediate sigma-phenylethinyl cation [(eta(5)-C5H5(CO)(2)Mn-C=C-Ph](+) to a binuclear dication of bis-carbine type (eta(5)-C5H5(CO)(2)Mn(+)dropC-C(Ph)=C(Ph)-CdropMn(+)(CO)(2)(eta(5)-C5H5). The reduction of the latter leads to binuclear bis-vinylidene complex (eta(5) -C5H5)(CO)(2)Mn=C=C(Ph)-C(Ph)=C=Mn(CO)(2)(eta(5)-C5H5). Oxidative dehydrodimerization of complexes (eta(5)-C5R5)(CO)(L)Mn=C=(H)Ph (R = H, L = PPh3; R = Me, L = CO) occurs through the immediate C-beta-C-beta coupling of radical cations {(eta(5)-C5R5)(CO)(L)Mn=C=C(H)Ph}(+.) and yields binuclear dication bis-carbine complexes (eta(5)-C5R5)(CO)(L)Mn(+)dropC-C(H)(Ph)-C(H)(Ph)-CdropMn(+)(CO)(L)(eta(5)-C5R5), whose reduction leads to neutral compounds (eta(5)-C5H5)(CO)(2)Mn=C=C(Ph)-C(Ph)=C=Mn(CO)(L)(eta(5)-C5H5). Complex (eta(5)-C5H5)(CO)(2)Mn=C=C(Ph)-C(Ph)=C=Mn(CO)(2)(eta(5)-C5H5) undergoes the oxidation-induced nucleophilic addition of water, forming cyclic bis-carbene product with a bridge heterocyclic ligand (mu-3,4-diphenyl-2,5-dihydro-2,5-diylidene)-bis-(eta(5)- cyclopentadienyidicarbonyl manganese).