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- Title
Thioether Iron Complexes [(X-SMe-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>)Fe(C<sub>6</sub>H<sub>6</sub>)] (X = 9 or 10) as Synthons of Neutral Ferracarborane Fragments.
- Authors
Vinogradov, Mikhail M.; Nelyubina, Yulia V.; Corsini, Maddalena; Fabrizi de Biani, Fabrizia; Kudinov, Alexander R.; Loginov, Dmitry A.
- Abstract
The demethylation reactions of the cyclohexadienyl complexes [(η-X-SMe2-7,8-C2B9H10)Fe(η5-C6H7)] {X = 9 ( 1a), 10 ( 1b); X is the number of the substituent position} with PhCH2SNa in N, N-dimethylformamide (DMF) and subsequent protonation by acetic acid lead to the iron-benzene complexes [(η-X-SMe-7,8-C2B9H10)Fe(η-C6H6)] ( 2a and 2b). The visible-light irradiation of 2a in the presence of tBuNC or [Cp*Fe(η- cyclo-P5)] (Cp* = pentamethylcyclopentadienyl) affords the neutral half-sandwich complex [(η-9-SMe-7,8-C2B9H10)Fe( tBuNC)3] ( 3) or the triple-decker complex [(η-9-SMe-7,8-C2B9H10)Fe(µ-η:η- cyclo-P5)FeCp*] ( 4). The reaction of 2b with (THF)W(CO)5 (THF = tetrahydrofuran) selectively gives the iron-tungsten dinuclear complex [(η-10-SMe{W(CO)5}-7,8-C2B9H10)Fe(η-C6H6)] ( 5). The structures of 2a, 4, and 5 were determined by X-ray diffraction. Electrochemistry revealed that the redox processes of the SMe-substituted ferracarboranes are cathodically shifted (by ca. 350 mV) with respect to the corresponding redox changes of the SMe2 analogs. The Fe-C6H6 bonding in 2a and the related benzene complexes [(η-9-SMe2-7,8-C2B9H10)Fe(η-C6H6)]+ and [(η-7,8-C2B9H11)Fe(η-C6H6)] was analyzed by energy-decomposition analysis.
- Subjects
SULFIDES; SULFUR compounds; CHEMICAL reactions; COMPLEX compounds; IRON; CARBORANES
- Publication
European Journal of Inorganic Chemistry, 2017, Vol 2017, Issue 38/39, p4627
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201700333