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

• Published in: Journal of organometallic chemistry Vol. 689; no. 14; pp. 2401 - 2410
• Main Authors: Lau, Man-Kit, Cheung, Ka-Man, Zhang, Qian-Feng, Song, Yinglin, Wong, Wing-Tak, Williams, Ian D., Leung, Wa-Hung
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 15.07.2004; Elsevier
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Cyclometalated complex; Iridium(III); Physical Sciences; Rhodium(III); Science & Technology; Sulfur ligands; Cyclometalated complex; Sulfur ligands; Iridium(III); Rhodium(III); ORTHO-METALATED COMPLEXES; IR(III) COMPLEXES; CRYSTAL-STRUCTURE; REACTIVITY; PHOTOPHYSICAL PROPERTIES; rhodium(III); iridium(III); NMR; cyclometalated complex; MONONUCLEAR; sulfur ligands; SPECTROSCOPY; RH; LUMINESCENT
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2004.04.033

Teatment of [M(Buppy) 2Cl] 2 with bidentate sulfur ligands S ∧S afforded the cyclometalated complexes [M(Buppy) 2(S ∧S)] (M=Ir or Rh; BuppyH=2-(4 ′- tert-butylphenyl)pyridine; S ∧S=Et 2NCS 2, S 2P(OMe) 2, N(PPh 2S) 2). Interactions of [M(Buppy) 2Cl] 2 with [WQ 4] 2− (Q=S or Se) afforded the trinuclear heterometallic complexes [{M(Buppy) 2} 2(μ-WQ 4)]. 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 2P(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.