We have investigated the reaction of isonitriles (RNC) with diene complexes of Ti, Zr, and Hf. Cp*(Cl)Ti(2,3-dimethylbutadiene) reacts with 2 equiv of RNC (R = tBu, 1-adamantyl) to give η1,η2-diimine complexes. Cp*(Cl)Ti(N,N-di-tBu-η1,η2-diimine), in the presence of pyridine, fragments to Cp*(Cl)Ti(NtBu)(NC5H5) and an α-methylene cyclopent-3-enimine. Cp*(Cl)Hf(2,3-dimethylbutadiene) has been reported to give a cyclic amidine complex when treated with 2 equiv of 2,6-dimethylphenyl isonitrile. By X-ray crystallography, however, we find that Cp*(Cl)Hf(2,3-dimethylbutadiene) and 2,6-dimethylphenyl isonitrile give instead a 2,5-diazahafnacyclopentane that features a σ-interaction between the C–C bond of a cyclopropane ring and the Hf. Cp*2Zr(2,3-dimethylbutadiene) inserts only one equivalent of RNC to give iminoacyl complexes.

Reaction of group 4 metallacyclopentenes with isonitriles

251st National Meeting (2016)

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