The First SiH 2 2+ Complex, Dihydridotetrakis(3‐picoline)silicon Dichloride–Tetrakis(chloroform), [H 2 Si(3pic) 4 ]Cl 2 · 4 CHCl 3 : 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 H 3 SiCl, H 2 SiCl 2 , and HSiCl 3 , whereas with 3‐picoline the two hypervalent silicon compounds H 2 SiCl 2 ‐(3pic) 2 and [H 2 Si(3pic) 4 ]Cl 2 · 4 CHCl 3 containing hexacoordinated Si atoms are formed. These complexes are in a chemical equilibrium with each other in chloroform solution, from which crystals of [H 2 Si(3pic) 4 ]Cl 2 · 4 CHCl 3 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 [H 2 Si(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 1 H 1 H ROESY experiment suggest that dissolution has no significant impact on the molecular structure of [H 2 Si(3pic) 4 ]Cl 2 · 4 CHCl 3 .