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|Title:||Reactions of the B-phenylborole complex [CpRh(eta5-C4H4BPh)] with metalloelectrophiles [(ring)M]2+||Authors:||Loginov, D. A.
Petrovskii, P. V.
Starikova, Z. A.
Fabrizi De Biani, Fabrizia
Kudinov, A. R.
|Issue Date:||2005||Project:||None||Journal:||EUROPEAN JOURNAL OF INORGANIC CHEMISTRY||Abstract:||
Thirty-valence-electron dicationic triple-decker complexes with a bridging borole ligand [CpRh(μ-η5:η5-C4H4BPh)M(ring)]2+ [M(ring) = CoCp* (3), IrCp* (6), Ru(η-C6H3Me3-1,3,5) (8a), Ru(η-C6Me6) (8b)] were obtained by stacking reactions of [CpRh(η5-C4H4BPh)] (2) with the corresponding half-sandwich fragments [M(ring)]2+. Minor formation of arene-type complexes [CpRh(μ-η5:η6-C4H4BPh)M(ring)]2+ was observed for M(ring) = IrCp* and Ru(arene). On the contrary, the arene-type complex [CpRh(μ-η5:η6-C4H4BPh)RhCp*]2+ (5) was isolated as the sole product from the reaction of 2 with the fragment [RhCp*]2+; an intermediate formation of the triple-decker complex [CpRh(μ-η5:η5-C4H4BPh)RhCp*]2+ (4) in this reaction was detected by 1H NMR spectroscopy. Heating 6 in nitromethane gives the symmetrical triple-decker complex [Cp*Ir(μ-η5:η5-C4H4BPh)IrCp*]2+ (10). The cations were isolated as salts with the BF4– anion. The structures of 2, 5(BF4)2, 6(BF4)2 and 8a(BF4)2 were determined by X-ray diffraction. The electrochemical properties of the complexes were also investigated.
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