63339-35-5Relevant academic research and scientific papers
Organic syntheses via transition metal complexes. 78. Hydrazinolysis of alkynylcarbene complexes of chromium and tungsten. Formation of hydrazinocarbene, imidate, pyrazolidinylidene, and nitrile complexes
Aumann, Rudolf,Jasper, Beate,Fr?hlich, Roland
, p. 2447 - 2455 (1995)
Hydrazinolysis of alkynylcarbene complexes (CO)5M=C(OEt)C≡Ph (1, M = W; 1′, M = Cr) with mono- and 1,2-dimethylhydrazine MeHNNHR (2a,b) (R = Me, H) affords three different-type compounds: hydrazinocarbene complexes (CO)5M=C(NMe-NHR)C≡CPh [(E/ Z)-3a,b], imidate complexes (CO)5M[MeN=C(OEt)-C≡CPh] [(E/Z)-4a], and pyrazolidinylidene complexes 5a,b. Hydrazinolysis of 1/1′ with 1,1-dimethylhydrazine or (unsubstituted) hydrazine H2NNR2 (2c,d) (R = Me, H) yields hydrazinocarbene complexes (CO)5M=C(NH-NR2)C≡CPh [(E/Z)-3c], imidate complexes (CO)5M[HN=C(OEt)C≡CPh] [(E/Z)-4a], and benzonitrile complexes (CO)5M(N≡CPh) (8). Hydrazinolysis of 1 with H2NNHR (2e,f) (R = COMe, Ph) gives pyrazoles 12e,f as the only products. The product composition of the reactions of 2a-d with 1 is markedly influenced by the reaction temperature. Reaction of 1 with N- and O-methylhydroxylamines (13, 14) affords imidate complexes 4 only. The hydrazinocarbene complexes (E)-3a and (Z)-3c were characterized by X-ray diffraction. Both compounds crystallize in space group P1 (No. 2): (E)-3a, C16H12N2O5W, cell parameters a = 8.501(2) ?, b = 9.645(2) ? c = 11.860(2) ?, α = 103.56(2)°, β = 95.59(2)°, γ = 111.76(2)°, Z = 2, R1 = 0.043, and wR2 = 0.083; (Z)-3c, C16H12N2O5W, cell parameters a = 9.380(3) ?, b = 9.685(4) ?, c = 10.804(3) ?, α = 84.77(5)°, β = 80.74(3)°, γ = 66.47(3)°, Z = 2, R1 = 0.036, and wR2 = 0.086.
