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. The labile nitromethane solvates [CpCo(μ-1,3-C3B2Me5)M(MeNO2)3]2+ {generated from the bromide complexes [CpCo(μ-1,3-C3B2Me5)MBr2]2 (M = Rh, Ir; Cp = cyclopentadienyl) and AgBF4 in MeNO2} react with arenes to give triple-decker complexes [CpCo(μ-1,3-C3B2Me5)M(arene)]2+. X-ray diffraction, electrochemical techniques and DFT calculations were used for the characterization of the complexes obtained

Muratov, D.V., Romanov, A.S., Loginov, D.A., Corsini, M., FABRIZI DE BIANI, F., Kudinov, A.R. (2015). Dicationic μ-diborolyl arene triple-decker complexes [CpCo(μ-1,3-C<inf>3</inf>B<inf>2</inf>Me<inf>5</inf>)M(arene)]<sup>2+</sup> (M = Rh, Ir; Cp = cyclopentadienyl): Synthesis, structures, electrochemistry and bonding. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2015(5), 804-816 [10.1002/ejic.201402927].

Dicationic μ-diborolyl arene triple-decker complexes [CpCo(μ-1,3-C3B2Me5)M(arene)]2+ (M = Rh, Ir; Cp = cyclopentadienyl): Synthesis, structures, electrochemistry and bonding

CORSINI, MADDALENA;FABRIZI DE BIANI, FABRIZIA;
2015-01-01

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. The labile nitromethane solvates [CpCo(μ-1,3-C3B2Me5)M(MeNO2)3]2+ {generated from the bromide complexes [CpCo(μ-1,3-C3B2Me5)MBr2]2 (M = Rh, Ir; Cp = cyclopentadienyl) and AgBF4 in MeNO2} react with arenes to give triple-decker complexes [CpCo(μ-1,3-C3B2Me5)M(arene)]2+. X-ray diffraction, electrochemical techniques and DFT calculations were used for the characterization of the complexes obtained
Muratov, D.V., Romanov, A.S., Loginov, D.A., Corsini, M., FABRIZI DE BIANI, F., Kudinov, A.R. (2015). Dicationic μ-diborolyl arene triple-decker complexes [CpCo(μ-1,3-C<inf>3</inf>B<inf>2</inf>Me<inf>5</inf>)M(arene)]<sup>2+</sup> (M = Rh, Ir; Cp = cyclopentadienyl): Synthesis, structures, electrochemistry and bonding. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2015(5), 804-816 [10.1002/ejic.201402927].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11365/983459