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- Title
Dicationic μ-Diborolyl Arene Triple-Decker Complexes [CpCo(μ-1,3-C<sub>3</sub>B<sub>2</sub>Me<sub>5</sub>)M(arene)]<sup>2+</sup> (M = Rh, Ir; Cp = Cyclopentadienyl): Synthesis, Structures, Electrochemistry and Bonding.
- Authors
Muratov, Dmitry V.; Romanov, Alexander S.; Loginov, Dmitry A.; Corsini, Maddalena; Fabrizi de Biani, Fabrizia; Kudinov, Alexander R.
- Abstract
The reaction of the bromide complexes [CpCo(μ-1,3-C3B2Me5)MBr2]2 [M = Rh ( 1), Ir ( 2); Cp = cyclopentadienyl] with AgBF4 in acetonitrile affords the tris(acetonitrile) μ-diborolyl triple-decker complexes [CpCo(μ-1,3-C3B2Me5)M(MeCN)3]2+ [Rh ( 3), Ir ( 4)]. The labile nitromethane solvates [CpCo(μ-1,3-C3B2Me5)M(MeNO2)3]2+, generated in a similar way, react with benzene and its methylated derivatives to give the arene triple-decker complexes [CpCo(μ-1,3-C3B2Me5)M(arene)]2+ [M = Rh ( 5), Ir ( 6); arene = C6H6 ( a), 1,2,4,5-Me4C6H2 ( b), C6Me6 ( c)]. The structures of 5b(BF4)2, 5c(BF4)2, 6b(BF4)2 and 6c(BF4)2 were determined by X-ray diffraction. The electron-transfer ability of the arene complexes was ascertained by electrochemical techniques. In general, they are able to undergo two separate one-electron reductions reversibly. DFT calculations revealed structural changes caused by redox processes and satisfactorily predicted the redox potentials. The second reduction is accompanied by a η6 → η4 hapticity change of the arene ligand. Energy decomposition analysis revealed that the Rh-benzene bond in cation 5a is weaker than in cyclopentadienyl analogues [(C5R5)Rh(C6H6)]2+; however, 5a proved to be the least reactive in benzene replacement with acetonitrile and mesitylene.
- Subjects
CATIONS; AROMATIC compound synthesis; CHEMICAL synthesis; METHYLATION; ELECTROCHEMICAL research
- Publication
European Journal of Inorganic Chemistry, 2015, Vol 2015, Issue 5, p804
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201402927