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

Abstract Diarylallenylidene(pentacarbonyl)-chromium and -tungsten complexes, (CO) 5 MCCCR 2 (M  W ( 1 ), Cr ( 2 )), react with amines, imines and hydrazines by addition of the nitrogen nucleophile to the C α allenylidene atom. With NEt 3 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 HNEt 2 or H 2 NPh gives alkenyl(amino)carbene complexes, (CO) 5 MC [C(H)CR 2 ] NR′ 2 ( 3–5 ); (b) of 1 and 2 with HNCR 2 gives alkenyl(alkylideneamino)carbene complexes, (CO) 5 MC[C(H)CR 2 ] [NCR′ 2 ] ( 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) 5 WC[C(H)CR 2 ] [N(Me)N(R)H] ( 11 ) and (e) of 1 with H 2 NNR 1 R 2 (R 1  R 2  H, Me; R 1  H, R 2  Ph) alkenyl(amino)carbene complexes ( 13 ) and/or aciylnitrile complexes, (CO) 5 W[N  C C(H)CR 2 ] ( 12 ). The structures of representative examples of 6 , 11 and 12 were established by X-ray analyses.