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

Abstract

Treatment of [M(Buppy) 2Cl] 2 (M=Ir (1), Rh (2); BuppyH=2-(4′-tert-butylphenyl)pyridine) with Na(Et 2NCS 2), K[S 2P(OMe) 2], and K[N(Ph 2PS) 2] 2 afforded monomeric [Ir(Buppy) 2 (S ∧S)] (S ∧S=Et 2NCS 2 (3), S 2 P(OMe) 2 (4), N(PPh 2S) 2 (5)) and [Rh(Buppy) 2(S ∧S)] (S ∧ S=Et 2NCS 2 (6), S 2P(OMe) 2 (7), N(PPh 2S) 2 (8)), respectively. Reaction of 1 with Na[N(PPh 2Se) 2] gave [Ir(Buppy) 2 {N(PPh 2Se) 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 [Et 4N] 2[WQ 4] gave trinuclear heterometallic complexes [{Ir(Buppy) 2} 2 (μ-WQ 4)] (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(μ 3-S)}] (16) that has been characterized by X-ray diffraction. © 2004 Elsevier B.V. All rights reserved.