Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
The bis(ethene) complex [Tp*Ir-(C2H4)2] (1*) (Tp* = tris(3,5-dimethyl-1-pyrazol-1-yl)hydroborato) undergoes thermal rearrangement to the hydrido-allyl complex [Tp*IrH(π3-C3H4Me)] (6*), through the intermediacy of the hydrido-vinyl complex [Tp*IrH(C2H3)(C2H4)] (2*). The overall conversion of 1* into 6* corresponds formally to the dimerisation of ethene by an unprecedented pathway that involves sequential C-H bond activation of a coordinated olefin molecule and C-C bond formation by coupling of the resulting vinyl and ethene moieties. Similar transformations have been observed for monosubstituted olefins like propene and 1-butene, while the internal alkene cis-2-butene experiences allylic activation of an sp3 C-H bond, which provides an alternative route to 6*. The extension of these investigations to the analogous complexes of the unsubstituted tris(pyrazolyl)hydroborato ligand Tp is also reported. Mechanistic studies on the formation of the C-C bond by coupling of the vinyl and the olefin ligands suggest the participation of a vinylidene complex (formed by α-H abstraction from the vinyl group), which then rearranges to an allene species. Evidence for the involvement of these and other key reaction intermediates is provided.
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