198215-33-7

Upstream product

• 198215-34-8 [(η(5)-C5Me5)Ir(μ-SCy)2Ir(η(5)-C5Me5)] 
• 76-05-1 trifluoroacetic acid 

Relevant academic research and scientific papers

Preparation of a series of dinuclear Ir(III) and Ir(II) complexes containing bridging thiolate ligands

Reactions of [Cp*IrCl(μ-Cl)2IrCp*Cl] (Cp* = η5-C5Me5) with RSH in CH2Cl2 at room temperature afforded two types of thiolatebridged dinuclear Ir(III) complexes, [Cp*IrCl(μ-SR)2IrCp*Cl] (2; R = Pr1, Cy, CH2Ph; Cy = cyclohexyl) or [Cp*Ir(μ-SEt)3IrCp*]Cl, depending upon the nature of the substituent R. Reduction of 2 (R = Pr1 (2a), Cy) with excess Na-Hg in THF resulted in the formation of the dinuclear Ir(II) complexes [Cp*Ir(μ-SR)2IrCp*] (3). X-ray diffraction studies were undertaken for 2a and 3b (R = Cy) to determine their detailed structures. 2a: C26H44Cl2S2Ir2, space group C2/c, a = 21.255(8), b = 8.606(6), c = 17.788(6) A?, β = 118.39(2)°, Z = 4. 3b: C32H52S2Ir2, space group P2/n, a = 8.912(6), b = 11.224(6), c = 16.496(6) A?, β = 97.78(4)°, Z=2. Complexes 3 reacted with CF3COOH to give the cationic Ir(III) complexes having a bridging hydride ligand [Cp*Ir(μ-H) (μ-SR)2IrCp*] [OCOCF3].

Synthesis of diiridium complexes containing bridging thiolate and thioether ligands [(η5-C5Me5)Ir(μ-SR) (μ-MeSR) -Ir(η5-C5Me5)] [OSO2CF3] (R-Pri, cyclohexyl) and their reactivities toward CO and H2

Treatment of [Cp*Ir(μ-SR)2IrCp*] (Cp* = η5-C5Me5, R = Pri, Cy; Cy = cyclohexyl) with MeOTf (OTf=OSO2CF3) afforded the thiolate- and thioether-bridged diiridium complexes [Cp*Ir(μ-SR) (μ-MeSR) IrCp*] [OTf] (3). Upon heating a THF solution of 3a (R = Pri) under N2, dissociation of the bridging MeSPri ligand took place and a coordinatively unsaturated complex [Cp*Ir(μ-SPri)IrCp*] [OTf] (4) was isolated in an analytically pure form, and characterized spectroscopically. When 3a was treated analogously under CO, a diiridium carbonyl complex [Cp*Ir(CO) (μ-SPri) IrCp* (CO)] [OTf] (5) was obtained in 53percent yield together with 4 (39percent yield). On the other hand, reactions of 3 with H2 under similar conditions resulted in the formation of diiridium complexes bridged by two hydride and one thiolate ligands [Cp*Ir(μ-H)2(μ-SR)IrCp*] [OTf] (6) in high yields. The structure of 6 was determined by X-ray analysis using a single crystal of [Cp*Ir(μ-H)2(μ-SCy)IrCp*] [BPh4] derived from 6b (R=Cy).