19705-90-9Relevant articles and documents
Transformation of aziridinocarbene complexes of chromium and tungsten into nitrile complexes and olefins
Denise, B.,Parlier, A.,Rudler, H.
, p. C23 - C32 (1988)
Carbene complexes of chromium and of tungsten bearing the methylaziridine group on the carbene carbon atom undergo a thermal rearrangement with elimination of propene to give nitrile complexes of the metals.
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 (2008/10/09)
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.
Formal nitrogen hydride insertion into the metal-carbene bond of fischer-type carbene complexes
Raubenheimer, Helgard G.,Kruger, Gert J.,Scott, Fred,Otte, Ronald
, p. 1789 - 1795 (2008/10/08)
A series of imidate complexes [(CO)5M{NH=C(OR1)R2)] (M = W, R1 = Me or Et, R2 = Ph; M = W, R1 = Me, R2 = Me; M = Cr, R1 = Me or Et, R2 = Ph) can be prepared by reaction of alkoxyorganocarbene complexes with S,S-diphenylsulfilimine, NH=SPh2. The thiocarbene complex [(CO)5W{C(SPh)R2)] (R2 = Me) similarly gives the corresponding thioimidate complex, but when R2 = Ph, [(CO)5W(NCPh)] (9) is the only product. The heterometallocyclic complex [(CO)4W{C(OEt)C(OEt)=CS(CH2)3S}] also undergoes NH insertion and concomitant chelate ring enlargement. The imidate complex [(CO)5W{NH=C(OMe)Ph}] (1) is deprotonated by Bu-, H-, MeO-, and RS- to afford the nitrile (9), but with dimethylamine the amidine complex [(CO)5W{NH=C(NMe2)Ph}] (13) is formed by aminolysis. The Z isomer of 1 and the E isomer of 13 are completely characterized by X-ray structure determinations. Crystal data for 1: WC13H9NO6, Mr 459.07, monoclinic, space group P21/c, a = 10.694 (4) ?, b = 6.650 (1) ?, c = 20.338 (4) ?, β = 92.18 (3)°, V = 1445 ?3, Z = 4, Dcalcd = 2.11 g cm-3. Crystal data for 13: WC14H12N2O5, Mr 472.118 monoclinic, space group P21/c, a = 11.723 (2) ?, b = 9.550 (1) ?, c = 15.032 (6) ?, β = 105.43 (3)°, V = 1622 ?3, Z = 4, Dcalcd = 1.93 g cm-3. The W-N(sp2) bond lengths are 2.249 (5) and 2.243 (5) ?. Reaction of NH=SPh2 with [M(CO)6] (M = Cr or W) produces yellow solutions from which [(CO)5M(SPh2)] can be isolated. In the presence of PPh3 only the monosubstituted phosphine complexes form in less than 50% yields.
