Versatile Tautomerization of EH2‑Substituted Silylenes (E = N, P, As) in the Coordination Sphere of Nickel

The synthesis and tautomerization of a “half-parent” aminosilylene and its heavy P- and As-analogues (TMSLSi-EH2; E = N, P, As; TMSL = N­(SiMe3)­(2,6-iPr2C6H3)) in the coordination sphere of nickel(0) to give the corresponding side-on η2-RSi­(H)EH and RH2Si-E (“silylpnictinidene”) nickel complexes are reported. These complexes can be accessed through salt metathesis reactions of the lithium dihydropnictides LiEH2 with the acyclic chlorosilylene nickel(0) complex 1, [TMSL­(Cl)­Si → Ni­(NHC)2; NHC = :C­[(iPr)­NC­(Me)]2). In addition, we report the facile E–H bond activation reactions of EH3 with 1, which furnished a silyl nickel­(II) complex through NH3 activation, but phosphido and arsenido complexes in the activation of PH3 and AsH3, respectively. Notably, reaction of 1 with LiNH2 leads to the acyclic bis­(amido)­silylene complex [TMSL­(H2N)Si → Ni­(NHC)2] 5, which does not undergo N–H proton migration to silicon­(II) under ambient conditions. The transformation of the P- and As-analogues of 1 furnishes directly the respective side-on SiE Ni complexes (nickelacycles), [η2-{TMSL­(H)­SiE­(H)}­Ni­(NHC)2] (E = P, 6; E = As, 9). These nickelacycles show a vastly different stability in solutions. While 6 is stable for several days at ambient temperature, 9 undergoes further rearrangement processes within minutes of its formation. Given the high acidity of the As–H proton in 9, however, this moiety can be trapped as a highly charge separated metalated-η2-silaarsene nickel complex 12 that is best described as an [AsSiNi] nickelacycle with Si–As multiple bond character. Taken as a whole, these results give, for the first time, insights into the relative stability of the tautomeric forms of side-on silaldimine transition metal complexes. The electronic nature and the rearrangement processes of these compounds were also investigated by quantum chemical calculations.