Steering S-H and N-H bond activation by a stable n-heterocyclic silylene: different addition of H(2)S, NH(3), and organoamines on a silicon(II) ligand versus its Si(II)-->Ni(CO)(3) complex.

The strikingly different behavior of the ylide-like, N-heterocyclic silylene LSi: (5: L = CH[(C horizontal lineCH(2))CMe(NAr)(2)]; Ar = 2,6-(i)PrC(6)H(3)) versus its LSi-->Ni(CO)(3) complex 13 to activate E-H bonds (E = S, N) of small molecules is reported. Remarkably, conversion of 5 with hydrogen sulfide leads exclusively to the first isolable silathioformamide, L'Si( horizontal lineS)H (16: L' = CH[C(Me)NAr](2); Ar = 2,6-(i)PrC(6)H(3)) with a donor-supported Si horizontal lineS double bond and four-coordinate silicon. The latter result demonstrates the unusual ambivalent reactivity of 5 by combining two modes of reactivity involving S-H bond activation and subsequent 1,4- and 1,1-addition, respectively. In addition, 5 can serve as a ligand with well-balanced sigma-donor and pi-acceptor capabilities toward transition metals. This has been demonstrated by the isolable [Ni(0)(arene)] complexes 12a-e (arene = Me(n)C(6)H(6-n), n = 0-3), which are ideal precursors for the formation of the corresponding Ni(CO)(3) complex 13. The latter activates a S-H bond in hydrogen sulfide, too, but the presence of the Ni(CO)(3) moiety governs the formation of the complex 17, bearing an unprecedented beta-diketiminate silicon(II) thiol ligand: L'Si(SH): (L' = CH[C(Me)NAr](2); Ar = 2,6-(i)PrC(6)H(3)). Likewise, the Si(II)-->Ni(CO)(3) coordination in 13 steers exclusively 1,4-addition of ammonia, isopropylamine, and phenylhydrazine onto the silylene ligand 5, leading to the corresponding beta-diketiminate silicon(II) amide or hydrazide complexes L'Si(NHR)-->Ni(CO)(3) (23a-c: R = H, (i)Pr, N(H)Ph). IR measurements reveal that the carbonyl stretching frequencies of the Ni(CO)(3) moiety in 23a-c are shifted to even lower wavenumbers in comparison to those of NHCs or phosphines. In other words, the beta-diketiminate silicon(II) amide ligands in 23a-c represent the strongest donors in the series of N-heterocyclic silylenes reported as yet.