SYNTHESIS, CHARACTERIZATION, AND REACTION CHEMISTRY OF NEW TRIFLUOROMETHANESULFONATO COMPLEXES OF RHODIUM AND IRIDIUM - FORMATION OF CATIONIC RH-PT AND IR-PT HETEROBINUCLEAR COMPLEXES WITH BRIDGING CHLORIDE LIGANDS

Reactions of (eta(5)-C5Me5)M(PMe3)(Cl)2 (M = Rh, 1; M = Ir, 2) with excess AgOTf in CH2Cl2 give bis(triflate) complexes (eta(5)-C5Me5)M(PMe3)(OTf)2 (M = Rh, 3; M = Ir, 4). Complexes 3 and 4 undergo facile reactions with CH3CN affording bis(acetonitrile) complexes [(eta(5)-C5Me5)M(PMe3)(CH3CN)2]2+[OTf]2- (M = Rh, 5; M = Ir, 6). Reactions of (eta(5)-C5Me5)Rh(PMe3)(OTf)2 (3) with cis-Pt(Cl)2(PR3)2 ((PR3)2 = Ph2P(CH2)3PPh2, 7; PR3 = PPh3, 8) generate heterobinuclear Rh-Pt complexes [(eta(5)-C5Me5)(PMe3)Rh(mu-Cl)2Pt(PR3)2]2+[OTf]2-(9, 11). Likewise, reactions of (eta(5)-C5Me5)Ir(PMe3)(OTf)2 (4) with cis-Pt(Cl)2(PR3)2 (7, 8) result in the formation of heterobinuclear Ir-Pt complexes [(eta(5)-C5Me5)(PMe3)Ir(mu-Cl)2Pt(PR3)2]2+[OTf]2- (10, 12). An unambiguous structural assigment for the heterobinuclear bridging chloride complexes 9-12 has been established by an X-ray diffraction study on complex [(eta(5)-C5Me5)(PMe3)Ir(mu-Cl)2Pt(Ph2P-(CH2)3PPh2)]2+[OTf]2- (10).