American Chemical Society
om0609721_si_002.cif (93.67 kB)

Synthesis of 16-Electron (η3-Cyclooctenyl)metallacarboranes of Rhodium(III) and Iridium(III) with the New Sterically Demanding [(4‘-MeC6H4)2C2B9H9]2- Carborane Ligand. Molecular Structures of [3-{(1−3-η3)-C8H13}-1,2-(4‘-MeC6H4)2-3,1,2-pseudocloso-MC2B9H9] (M = Rh, Ir) and [(η6-MeC6H4)Rh(C2B9H9C6H4Me)Rh(η4-C8H12)]2, a Dimeric Byproduct Containing Distorted 13-Vertex {4,9,1,10-Rh2C2B9} Cluster Units

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posted on 2020-04-02, 17:02 authored by Leonid S. Alekseev, Fedor M. Dolgushin, Alexander A. Korlyukov, Ivan A. Godovikov, Evgenii V. Vorontsov, Igor T. Chizhevsky
Reactions of the [K]+ salt of the [7,8-(4‘-MeC6H4)2-7,8-nido-C2B9H10]- monoanion with the COD−rhodium and COD−iridium μ-chloride complexes [(η4-COD)2M2(μ-Cl)2] proceed in benzene at ambient temperature with the formation of the 16-electron complexes [3-{(1−3-η3)-C8H13}-1,2-(4‘-MeC6H4)2-3,1,2-pseudocloso-MC2B9H9] (5, M = Rh(III); 6, M = Ir(III)), respectively, whose pseudocloso strucrure has been confirmed by single-crystal X-ray diffraction studies. The major species 5 is formed along with a small amount of the dimeric rhodacarborane [(η6-MeC6H4)Rh(C2B9H9C6H4Me)Rh(η4-C8H12)]2 (7), which, as found from X-ray structure determinations, is composed of two distorted {4,9,1,10-Rh2C2B9} cluster units joined together through η6 coordination of the 4-tolyl cage substituent of one unit to one of the rhodium atoms of the second unit and vice versa.