Nucleophilic addition and substitution reactions on the sulfur atoms bound to two Ir atoms. Conversion of a hydrosulfido complex [(η5-C5Me5)2Ir2(μ-SH)3]Cl into a series of diiridium complexes with bridging thiolato ligands

The hydrosulfido-bridged diiridium complex [Cp*Ir(μ-SH)3IrCp*]Cl 2 (Cp* = η5-C5Me5) reacted with an excess of CH2CHX (X = COMe, SO2Ph, COOMe, CN) in the presence of NEt3 (4 equiv) in MeCN to afford the diiridium complexes [Cp*Ir(μ-SCH2CH2X)3IrCp*]Cl 4, which contain three bridging thiolato ligands derived from the Michael addition of the μ-SH ligands in 2 to the activated alkenes. In contrast, when only 2 equiv of CH2CHX (X = SO2Ph, CN) were allowed to react with 2 under analogous conditions, sulfido–thiolato complexes [Cp*Ir(μ-S)(μ-SCH2CH2X)2IrCp*] 5 were obtained exclusively. Reaction of 5d (X = CN) with neat ClCH2CH2Cl and that of 2 with CH2CHCN in ClCH2CH2Cl in the presence of NEt3 both gave a mixed-thiolato complex [Cp*Ir(μ-SCH2CH2Cl)(μ-SCH2CH2CN)2IrCp*]Cl 6. Diiridium complexes with bridging dithiolato ligands were also obtainable from 2, which include [Cp*Ir(μ-SCH2CH2S)(μ-SCH2CH2Cl)IrCp*]Cl 7 from the reaction with ClCH2CH2Cl/NEt3 along with [Cp*Ir{μ-SCH2CH2CH(OH)S}(μ-SCH2CH2CHO)IrCp*]Cl and [Cp*Ir{μ-SCHPhCH2CH(OH)S}(μ-S)IrCp*] 9 afforded by treatment with α,β-unsaturated aldehydes CH2CHCHO and PhCHCHCHO, respectively. Reaction of 2 with ethylene sulfide in the presence of NEt3 also yielded a diiridium complex with bridging dithiolato ligands [Cp*Ir(μ-SCH2CH2S)2IrCp*] 10. Detailed structures have been determined by X-ray analyses for 4b (X = SO2Ph), 5d, 9, and 10, as well as the PF6 salts of 6 and 7.

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