The reaction of different Tp(Me2)Ir derivatives and dimethylacetylene dicarboxylate (DMAD) allows the preparation of three different metallacycloheptatriene complexes and an unusual allyl-terminated metallacycle. The C atoms of distant C=C bonds in the metallacycles, including aromatic ones, can be converted selectively to the corresponding keto functionality under mild conditions.
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C-H Bond activation and C-C bond formation in the reaction of 2,5-dimethylthiophene with TpMe2Ir compounds.
Dalton Trans
April 2005
Instituto de Investigaciones Químicas-Departamento de Química Inorgánica, Consejo Superior de Investigaciones Cientificas-Universidad de Sevilla, Avda. Américo Vespucio 49, Isla de la Cartuja, 41092, Sevilla, Spain.
The bulky 2,5-dimethylthiophene (2,5-Me2T) reacts at 60 degrees C with TpMe2Ir(C2H4)2 to give a mixture of two TpMe2Ir(III) hydride products, 3 and 4, that contain in addition a thienyl (3) or a thienyl-derived ligand (4). For the generation of 3 only sp2 C-H activation is needed, but the formation of 4 requires also the activation of an sp3 C-H bond and the formation of a new C-C bond (between vinyl and thienyl fragments). In the presence of 2,5-Me2T, compound 4 reacts further to produce a complex thiophenic structure (5, characterized by X-ray methods) that derives formally from two molecules of 2,5-Me2T and a vinyl fragment.
View Article and Find Full Text PDFCoupling of internal alkynes in tp(me2)ir derivatives: selective oxidation of a noncoordinated double bond of the resulting iridacycloheptatrienes.
J Am Chem Soc
February 2003
Instituto de Investigaciones Químicas, Consejo Superior de Investigaciones Científicas-Universidad de Sevilla, Avda, Spain.
The reaction of different Tp(Me2)Ir derivatives and dimethylacetylene dicarboxylate (DMAD) allows the preparation of three different metallacycloheptatriene complexes and an unusual allyl-terminated metallacycle. The C atoms of distant C=C bonds in the metallacycles, including aromatic ones, can be converted selectively to the corresponding keto functionality under mild conditions.
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