SYNTHESIS OF ORTHOMETALLATED RHODIUM(III) COMPOUNDS - CRYSTAL-STRUCTURES OF [RHCL2(ETA-2-(C6H4)PPH2)(ETA-2-DPPM)] AND (ETA-2-(C6H4)PPH2)(ETA-1-PCCL)(PHEN)](SBF6).CH2CL2 (DPPM=BIS(DIPHENYLPHOSPHINO)METHANE - PCCL=P(O-CLC6H4)-PH2 - PHEN=1,10-PHENANTHROLINE)

Neutral and cationic rhodium(III) metallated compounds containing a fo ur-membered ring are prepared by different synthetic methods: (i) from rhodium(I) compounds that contain the ligand P(o-ClC6H4)PPh2, by 2c-2 e intramolecular oxidative addition; (ii) from metallated dirhodium(II ) compounds; (iii) by ligand substitution in [RhCl2{eta2-(C6H4)PPh2}(e ta2-P(o-ClC6H4)Ph2}]. The crystal structures of [RhCl2{eta2-(C6H4)PPh2 }(eta2-dppm)] (2) and of the dichloromethane solvate of {eta2-(C6H4)PP h2}{eta1-P(o-ClCH4)Ph2}(phen)](SbF6) (11) have been determined by X-ra y diffraction methods. In both complexes the Rh atom is in the distort ed 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-ClC6H4)PPh2 phosphine behaves as a monodentate ligand.