Interligand H⋯Si interactions in tungsten silyl trihydride complexes

The dichloride complex Cp∗(Am)WCl2 (1, Am = [(iPrN)2CMe]−) reacted with the primary silanes PhSiH3, (p-tolyl)SiH3, (3,5-xylyl)SiH3, and (C6F5)SiH3 to produce the W(VI) (silyl)trihydrides Cp∗(Am)W(H)3(SiHPhCl) (2), Cp∗(Am)W(H)3(SiHTolylCl) (3), Cp∗(Am)W(H)3(SiHXylylCl) (4), and Cp∗(Am)W(H)3[SiH(C6F5)Cl] (5). In an analogous manner, 1 reacted with PhSiH2Cl to give Cp∗(Am)W(H)3(SiPhCl2) (6). Complex 6 can alternatively be quantitatively produced from the reaction of 2 with Ph3CCl. NMR spectroscopic studies and X-ray crystallography reveal an interligand H⋯Si interaction between one W–H and the chlorosilyl group, which is further supported by DFT calculations.

Graphical abstractTungsten (VI) silyl trihydride complexes were prepared from the reaction of Cp∗(Am)WCl2 (Am = [(iPrN)2CMe]−) with primary silanes. NMR spectroscopic studies and X-ray crystallography reveal an interligand H⋯Si interaction between one W–H and the chlorosilyl group, which is further supported by DFT calculations.Figure optionsDownload full-size imageDownload as PowerPoint slideResearch highlights► Synthesis and reactivity of W(VI) silyl trihydride complexes. ► Interligand Si⋯H interactions observed by NMR spectroscopy and X-ray crystallography. ► Multiple Si–H activations proposed for formation of such complexes.