Si-H bond activation at {(NHC)₂Ni⁰} leading to hydrido silyl and bis(silyl) complexes: a versatile tool for catalytic Si-H/D exchange, acceptorless dehydrogenative coupling of hydrosilanes, and hydrogenation of disilanes to hydrosilanes.

The unique reactivity of the nickel(0) complex [Ni2(iPr2Im)4(COD)] (1) (iPr2Im = 1,3-di-isopropyl-imidazolin-2-ylidene) towards hydrosilanes in stoichiometric and catalytic reactions is reported. A series of nickel hydrido silyl complexes cis-[Ni(iPr2Im)2(H)(SiH(n-1)R(4-n))] (n = 1, 2) and nickel bis(silyl) complexes cis-[Ni(iPr2Im)2(SiH(n-1)R(4-n))2] (n = 1, 2, 3) were synthesized by stoichiometric reactions of 1 with hydrosilanes H(n)SiR(4-n), and fully characterized by X-ray diffraction and spectroscopic methods. These hydrido silyl complexes are examples where the full oxidative addition step is hindered. They have, as a result of the remaining Si-H interactions, remarkably short Si-H distances and feature a unique dynamic behavior in solution. Cis-[Ni(iPr2Im)2(H)(SiMePh2)] (cis-5) shows in solution at room temperature a dynamic site exchange of the NHC ligands, H-D exchange with C6D6 to give the deuteride complex cis-[Ni(iPr2Im)2(D)(SiMePh2)] (cis-5-D), and at elevated temperatures an irreversible isomerization to trans-[Ni(iPr2Im)2(D)(SiMePh2)] (trans-5-D). Reactions with sterically less demanding silanes give cis-configured bis(silyl) complexes accompanied by the release of dihydrogen. These complexes display, similarly to the hydrido silyl complexes, interestingly short Si-Si distances. Complex 1 reacts with 4 eq. HSi(OEt)3, in contrast to all the other silanes used in this study, to give the trans-configured bis(silyl) complex trans-[Ni(iPr2Im)2Ni(Si(OEt)3)2] (trans-12). The addition of two equivalents of Ph2SiH2 to 1 results, at elevated temperatures, in the formation of the dinuclear complex [{(iPr2Im)Ni-μ(2)-(HSiPh2)}2] (6). This diamagnetic, formal Ni(I) complex exhibits a long Ni-Ni bond in the solid state, as established by X-ray diffraction. The capability of the electron rich {Ni(iPr2Im)2} complex fragment to activate Si-H bonds was applied catalytically in the deuteration of Et3Si-H to Et3Si-D employing C6D6 as a convenient deuterium source. Furthermore, we show that 1 serves as a catalyst for the acceptorless dehydrogenative coupling of Ph2SiH2 to the corresponding disilane Ph2HSi-SiHPh2 and trisilane Ph2HSi-Si(Ph)2-SiHPh2, and the coupling of PhSiH3 to give a mixture of cyclic and linear polysilanes with high polydispersity (M(w) = 1119; M(n) = 924; M(w)/M(n) = 1.2). The capability of 1 to catalyze the formal reverse reaction as well is demonstrated by the hydrogenation of disilanes. The hydrogenation of the disilanes Ph2MeSi-SiMePh2 and PhMe2Si-SiMe2Ph to the corresponding hydrosilanes Ph2MeSi-H and PhMe2Si-H, respectively, proceeds effectively in the presence of 1 under very mild conditions (room temperature, 1.8 bar H2 pressure).