65198-79-0Relevant academic research and scientific papers
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 (1987)
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.
