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DOI: 10.1039/A806538A (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 4211-4214

Synthesis of the homoleptic rhodium(III) complex [Rh(C6Cl5)3]. Molecular structures of [Rh(C6Cl5)3] and [Rh(C6Cl4–C6Cl4)(C6Cl5)(SC4H8)2]

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María P. García, M. Victoria Jiménez, Fernando J. Lahoz, José A. López and Luis A. Oro

Abstract

The arylation of [RhCl3(SC4H8)3] (SC4H8 = tetrahydrothiophene, tht) with the Grignard reagent MgCl(C6Cl5), under different reaction conditions, afforded the neutral rhodium(III) complexes [Rh(C6Cl5)3] 1 and [Rh(C6Cl4–C6Cl4)(C6Cl5)(tht)2] 2 as well as the paramagnetic rhodium(II) compound [Rh(C6Cl5)2(tht)2] 3. The homoleptic complex 1 can also be obtained by treatment of [P(CH2Ph)Ph3][RhCl(C6Cl5)3] with AgClO4. The complexes are stable to the air and moisture in the solid state and moderately stable in deoxygenated solutions. The crystal structures of compounds 1 and 2 have been determined. They display distorted octahedral environments. All C6Cl5 groups in 1 or one C6Cl5 group in 2 act as chelating ligands being bonded through the ipso-C atom and one of the ortho-Cl atoms. Complex 2 additionally incorporates two tetrahydrothiophene ligands and a perchloro-2,2′-biphenylene ligand, formed by coupling of two pentachlorophenyl groups.

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