The First SiH Complex, Dihydridotetrakis(3‐picoline)silicon Dichloride–Tetrakis(chloroform), [H2Si(3pic)4]Cl2 · 4 CHCl3: Formation, Chemical Equilibria, and Structural Investigation by NMR Spectroscopy and Single‐Crystal X‐ray Diffraction

Bis(dichlorosilyl)amine reacts in chloroform solution with 2‐picoline to give H3SiCl, H2SiCl2, and HSiCl3, whereas with 3‐picoline the two hypervalent silicon compounds H2SiCl2‐(3pic)2 and [H2Si(3pic)4]Cl2 · 4 CHCl3 containing hexacoordinated Si atoms are formed. These complexes are in a chemical equilibrium with each other in chloroform solution, from which crystals of [H2Si(3pic)4]Cl2 · 4 CHCl3 could be isolated. The crystal structure of the latter was determined by single‐crystal X‐ray diffraction. The complex can be regarded as an “contact ion trio” of [H2Si(3pic)4]2+ and two Cl– ions. The N–Si bond lengths, r(Si–N) = 196.9(3) and 197.5(3) pm, are similar to those found in neutral hexacoordinated Si complexes. The data obtained from a 1H1H ROESY experiment suggest that dissolution has no significant impact on the molecular structure of [H2Si(3pic)4]Cl2 · 4 CHCl3.