Iridium(III) and rhodium(III) cyclometalated complexes containing sulfur and selenium donor ligands

Treatment of [M(Buppy)2Cl]2(M=Ir (1), Rh (2); BuppyH=2-(4′-tert-butylphenyl)pyridine) with Na(Et2NCS2), K[S2P(OMe)2], and K[N(Ph2PS)2]2afforded monomeric [Ir(Buppy)2(S∧S)] (S∧S=Et2NCS2(3), S2P(OMe)2(4), N(PPh2S)2(5)) and [Rh(Buppy)2(S∧S)] (S∧S=Et2NCS2(6), S2P(OMe)2(7), N(PPh2S)2(8)), respectively. Reaction of 1 with Na[N(PPh2Se)2] gave [Ir(Buppy)2{N(PPh2Se)2}] (9). The crystal structures of 3, 4, 7, and 8 have been determined. Treatment of 1 or 2 with AgOTf (OTf=triflate) followed by reaction with KSCN gave dinuclear [{M(Buppy)2}2(μ-SCN)2] (M=Ir (10), Rh (11)), in which the SCN-ligands bind to the two metal centers in a μ-S,N fashion. Interaction of 1 and 2 with [Et4N]2[WQ4] gave trinuclear heterometallic complexes [{Ir(Buppy)2}2(μ-WQ4)] (Q=S (12), Se (13)) and [{Rh(Buppy)2}2{(μ-WQ)4}] (Q=S (14), Se (15)), respectively. Hydrolysis of 12 led to formation of [{Ir(Buppy)2}2{W(O)(μ-S)2(μ3-S)}] (16) that has been characterized by X-ray diffraction.