356788-45-9Relevant academic research and scientific papers
C-N coupling reactions of allenes and methylacetylenes with an imidotitanium complex
Tr?sch, Dominique J.M.,Collier, Philip E.,Bashall, Alan,Gade, Lutz H.,McPartlin, Mary,Mountford, Philip,Radojevic, Sanja
, p. 3308 - 3313 (2001)
Reaction of the imidotitanium complexes [(N2Npy-κ3N)Ti(-NtBu)(py)] (1) and [(N2Npy-κN)Ti(=NtBu)] (1a) (N2Npy = (2-C5H4N)C(Me)CH2NSiMe3)2 ) with 2-butyne and 1-phenyl-propyne led to C-N coupling with the imido ligand and yielded the four-membered titanaazetidines [(N2Npy-κ3N)Ti{N(tBu)C(CHCH3) CH2}] (2) and [(N2Npy-κ3N)Ti{N(tBu)C-(CHC6H5 )CH2}] (3), respectively. The same reaction products were obtained in 2 + 2 cycloaddition reactions of 1 and 1a with 1,2-butadiene and phenylallene. The four-membered metallacycle with an exocyclic C=C double bond was established by X-ray diffraction studies of both compounds. A mechanism to explain the observed products from both types of reactions is proposed. Whereas the reactions of 1 with CO2, tBuNCO, and PhNCO were highly unspecific and did not lead to an isolable product, the conversion with the sterically encumbered isocyanate 2,6-iPr2C6H3NCO yielded the product of 2 + 2 cycloaddition to the Ti=N bond, namely [(N2Npy-κ3N)Ti{N(tBu)C(N-2,6-C6 H3iPr2)O}(py)] (4), the structure of which was elucidated by NMR spectroscopy.
