Reactions of Cp{sub *}Ir(2,5-dimethylthiophene) with Ru{sub 3}(CO){sub 12}, Re{sub 2}(CO){sub 10}, Mn{sub 2}(CO){sub 10}, and [({eta}{sub 6}-C{sub 6}H{sub 6})RuCl{sub 2}]{sub 2}
- Ames Lab., IA (United States)
Reactions of the isomers Cp{sub *}Ir({eta}{sub 4}-2,5-Me{sub 2}T) (1) and Cp{sub *}Ir(C,S-2,5-Me{sub 2}T) (2), where 2,5-Me{sub 2}T is 2.5-dimethylthiophene, with Ru{sub 3}(CO){sub 12}, Re{sub 2}(CO){sub 10}, Mn{sub 2}(CO){sub 10}, and [{eta}{sub 6}-C{sub 6}H{sub 6})RuCl{sub 2}]{sub 2} yield a remarkable diversity of products. With Ru{sub 3}(CO){sub 12}, both 1 and 2 give the CO-substituted product Cp{sub *}Ir{eta}{sub 4}-2,5-Me{sub 2}T.Ru{sub 3}(CO){sub 11} (4), in which the 2,5-Me{sub 2}T group is {eta}{sub 4}-coordinated to the Ir and S-coordinated to a Ru in the plane of the triangular Ru{sub 3}(CO){sub 11} cluster. With Re{sub 2}(CO){sub 10}, 1 reacts to give the CO-substituted product Cp{sub *}Ir({eta}{sub 4}-2,5-Me{sub 2}T.Re{sub 2}(CO){sub 9}) (6), in which 1 is S-coordinated in an equatorial position of the metal-metal dimer Re{sub 2}(CO){sub 9}. However, another product of this reaction is Cp{sub *}Ir({eta}{sub 4}-SC{sub 3}H{sub 2}MeC(=O)Me)[Re{sub 2}-(CO){sub 9}] (7), in which the 2,5-Me{sub 2}T ligand has been converted to a ring-opened acyl-thiolate unit that is S-coordinated to Re{sub 2}(CO){sub 9}. Compound 7 is the major product of the reaction of 2 with Re{sub 2}(CO){sub 10}. The reaction of 2 with Mn{sub 2}(CO){sub 10} gives Cp{sub *}Ir({eta}{sub 4}SC{sub 3}H{sub 2}MeC(=O)Me)[Mn{sub 2}(CO){sub 9}] (9), the Mn analog of 7. The reaction of [({eta}{sub 6}-C{sub 6}H{sub 6})RuCl{sub 2}]{sub 2} with 1 gives the product Cp{sub *}Ir({eta}{sub 4}-2,5-Me{sub 2}T.Ru({eta}{sub 6}-C{sub 6}H{sub 6})Cl{sub 2} (10), which illustrates again the strong S-donor ability of the Cp{sub *}Ir({eta}{sub 4}-2,5-Me{sub 2}T) (1), group. 39 refs., 3 figs., 4 tabs.
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 263129
- Journal Information:
- Organometallics, Vol. 15, Issue 12; Other Information: PBD: 11 Jun 1996
- Country of Publication:
- United States
- Language:
- English
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