6533b85ffe1ef96bd12c2449

RESEARCH PRODUCT

Synthesis of orthometallated rhodium(III) compounds. Crystal structures of [RhCl2{η2(C6H4)PPh2}(η2-dppm)] and [RhCl{η2(C6H4)PPh2}(η1-PCCl)(phen)] (SbF6)·CH2Cl2 (dppm=bis(diphenylphosphino)methane; PCCl=P(o-ClC6H4)Ph2; phen=1,10 phenanthroline)

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Abstract Neutral and cationic rhodium(III) metallated compounds containing a four-membered ring are prepared by different synthetic methods: (i) from rhodium(I) compounds that contain the ligand P( o -ClC 6 H 4 )PPh 2 , by 2c-2e intramolecular oxidative addition; (ii) from metallated dirhodium(II) compounds; (iii) by ligand substitution in [RhCl 2 {η 2 -(C 6 H 4 )PPh 2 }{η 2 -P( o -ClC 6 H 4 )Ph 2 }]. The crystal structures of [RhCl 2 {η 2 -(C 6 H 4 )PPh 2 }(η 2 -dppm)] ( 2 ) and of the dichloromethane solvate of [RhCl{η 2 -(C 6 H 4 )PPh 2 }{η 1 -P( o -ClC 6 H 4 )Ph 2 }(phen)](SbF 6 ) ( 11 ) have been determined by X-ray diffraction methods. In both complexes the Rh atom is in the distorted octahedral arrangement and the metallated phosphine forms, through P and C atoms, a four-membered ring with the metal. A dppm molecule in 2 and a phen molecule in 11 act also as chelating ligands. In 11 the P( o -ClC 6 H 4 )PPh 2 phosphine behaves as a monodentate ligand.