α-Addition von Aminen, Iminen und Hydrazinen an Allenyliden-Komplexe - Bildung von Carben-, Azetidinyliden- und Nitril-Komplexen

Article abstract of DOI:10.1016/0022-328X(93)83234-M

Diarylallenylidene(pentacarbonyl)-chromium and -tungsten complexes, (CO)5M=C=C=CR2 (M = W (1), Cr (2)), react with amines, imines and hydrazines by addition of the nitrogen nucleophile to the C_α allenylidene atom.With NEt3 the adduct formation is reversible.With secondary and primary amines, imines and hydrazines, the initially formed N-ylide complexes react readily further to give carbene, azetidinylidene and nitrile complexes, respectively.For example the reaction of (a) 1 and 2 with HNEt2 or H2NPh gives alkenyl(amino)carbene complexes, (CO)5M=CNR2' (3-5); (b) of 1 and 2 with HN=CR2' gives alkenyl(alkylideneamino)carbene complexes, (CO)5M=C (6,7); (c) of 1 with (i-Pr)N=C(Ph)H the azetidinylidene complex 9; (d) of 1 with 1,2-disubstituted hydrazines such as H(Me)NN(R)H (R = Me, Ph) alkenyl(hydrazino)carbene complexes, (CO)5W=C (11) and (e) of 1 with H2NNR¹R² (R¹ = R² = H, Me; R¹ = H, R² = Ph) alkenyl(amino)carbene complexes (13) and/or acrylnitrile complexes, (CO)5W(N<*>C-C(H)=CR2> (12).The structures of representative examples of 6, 11 and 12 were established by X-ray analyses.