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Salts of the bis(catecholato)borate anion with rhodium- and iridium-phosphine complex cations

Lookup NU author(s): Emeritus Professor Bill CleggORCiD, Dr Mark Elsegood, Dr Edward Robins


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In a series of five salts with rhodium- or iridium-phosphine complex cations {cis-chlorohydridotetrakis(triethylphosphine) iridium(III) bis(pyrocatecholato O,O')borate, [IrClH(C6H15P)(4)](C12H8BO4), (1); transchlorobis [ethylenebis(diphenylphosphine)]hydridorhodium(III) bis(pyrocatecholato-O,O')borate dichloromethane solvate, [RhClH(C26H24P2)(2)](C12H8BO4) . CH2Cl2, (2); trans-chlorobis[ethylenebis(dicyclohexylphos phine)]hydridorhodium(III) bis(pyrocatecholato-O,O')borate tetrakis(dichloromethane) solvate, [RhCIH(C26H48P2)(2)](C12H8BO4) . CH2Cl2, (3); tetrakis(trimethylphosphine)rhodium(I) bis(pyrocatecholato -O,O')borate, [Rh(C3H9P)(4)](C12H8BO4), (4); and cis-dihydridotetrakis(trimethylphosphine)rhodium(III) bis(pyrocatecholato O,O')borate, [RhH2(C3H9P)(4)](C12H8BO4), (5)}, the bis(catecholato)borate anion has approximate D-2d ((4) over bar 2m) symmetry, with the central spiro-B atom distorted from regular tetrahedral coordination geometry by reduction of the two intra-ring O-B-O bond angles. The two chelate rings show small deviations from planarity by folding about the O...O axis. The hydride and chloro ligands in the cation of compound (1), which has four monodentate phosphine ligands, are cis to each other, but in compounds (2) and (3), each with two chelating diphosphine ligands, they are mutually trans. The cation in compound (4) has only four phosphine ligands, which are arranged in a tetragonally distorted square-planar arrangement to minimise steric crowding. Its reaction product with molecular dihydrogen, compound (5), has a cis arrangement of the two hydride ligands in a distorted octahedral cation. The strong trans influence of the hydride ligands is reflected in lengthened bonds to the opposite ligands in each case.

Publication metadata

Author(s): Clegg W, Elsegood MRJ, Scott AJ, Marder TB, Dai CY, Norman NC, Pickett NL, Robins EG

Publication type: Article

Publication status: Published

Journal: Acta Crystallographica: Section C, Crystal Structure Communications

Year: 1999

Volume: 55

Issue: 5

Pages: 733-739

Print publication date: 01/05/1999

ISSN (print): 0108-2701

ISSN (electronic): 1600-5759

Publisher: Wiley-Blackwell Publishing, Inc.


DOI: 10.1107/S0108270199000323


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