Reactions of Cp*Ir(2,5-dimethylthiophene) with electrophiles, acids, and maleic anhydride

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This paper describes reactions of the two isomers (η 5-Cp*)Ir(η 4-2,5-Me 2T) ( 1) and (η 5-Cp*)Ir(C,S-2,5-Me 2T) ( 2), where 2,5-Me 2T is 2,5-dimethylthiophene, with several electrophiles, acids, and maleic anhydride. The reactions of 1 and 2 with methyl iodide give the same product Cp*Ir(η 4-2,5-Me 2T·CH 3) + in which the CH 3 + is bonded to the sulfur atom, as established by X-ray studies. The reaction of 1 with maleic anhydride gives two structurally characterized products: Cp*Ir[η 1(S)-Cp*Ir(η 4-2,5-Me 2T)][η 2-C 4H 2O 3] ( 13), in which S-coordinated Cp*Ir(η 4-2,5-Me 2T) and η 2-maleic anhydride are ligands to the Cp*Ir unit, and another product ( 12) that has the composition of 13 except for one additional oxygen atom. Complex 12, with a complicated and unusual structure, is also isolated from the reaction of maleic anhydride and the acylthiolate Cp*Ir[η 4-C 3H 2MeC(O)Me] ( 14). Reactions of 1 and 2 with a variety of other agents (MeSSMe 2 +, CF 3SO 3H, HCl, H 2S, EtOH and I 2) are also described.