New thioether-dithiolate complexes of Cp*Ir and some reactivity features

作者：Xu Chang; Li Yongxin; Goh Lai Yoong; Pullarkat Sumod A^*

来源：Journal of Organometallic Chemistry, 2012, 696(26): 4207-4214.

DOI：10.1016/j.jorganchem.2011.09.012

• Dithiolato-thioether ligand
• Cyclopentadienyl iridium
• Bimetallic complex
• Methylation

The reaction of [Cp*IrCl2](2) (Cp* = eta(5) - C5Me5) with the tridentate 3-thiapentane-1,5-dithiolate ligand, S(CH2CH2S-)(2) (tpdt), led to the formation of [Cp*Ir(eta(3) - tpdt)] (1) in 81% isolated yield. Subsequent reactions of 1 with [Cp*IrCl2](2) in 2:1 and 1:1 molar equiv ratios resulted in the formation of [Cp*Ir(mu - eta(2):eta(3) - tpdt) Cp*IrCl][PF6] (2) and [Cp*Ir mu - eta(2):eta(3) - tpdt) Cp*IrCl][Cp*IrCl3] (3) in 86 and 79% yields, respectively, based on 1, whereas the reactions of 1 with [(COD) IrCl](2) (COD = 1,5-cyclooctadiene) in 2:1 and 1:1 molar equiv ratios resulted in the formation of the homo-bimetallic derivatives Cp*Ir(mu - eta(1):eta(3) - tpdt)(COD)IrCl (4) (92% yield) and [Cp*Ir(mu - eta(2):eta(3) - tpdt)(COD)Ir] [(COD)IrCl2] (5) (82% yield). Reactions between 1 and [(COD)RhCl](2), yielded the hetero-bimetallic derivatives Cp*Ir(mu - eta(1):eta(3) - tpdt)(COD)RhCl (6) and [Cp*Ir(mu - eta(2):eta(3) - tpdt)(COD)Rh][(COD)RhCl2] (7), in 92 and 93% yields, respectively. The reaction of 1 with methyl iodide gave mono-methylated derivative [Cp*Ir(eta(3) - C4H8S3Me)]I (8) (93% yield). All these compounds have been comprehensively characterized.

• 出版日期2012-1-1
• 单位南阳理工学院