The First SiH22+ 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
✍ Scribed by Fleischer, Holger ;Hensen, Karl ;Stumpf, Thorsten
- Publisher
- Wiley (John Wiley & Sons)
- Year
- 1996
- Tongue
- English
- Weight
- 773 KB
- Volume
- 129
- Category
- Article
- ISSN
- 0009-2940
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✦ Synopsis
Bis(dichlorosi1yl)aminc / Dihydridotetrakis(3-picoline)silicon dichloride-tetrakis(ch1oroform) / Dative Si-N interaction / 'H'H ROESY Bis(dichlorosily1)amine reacts in chloroform solution with 2picoline to give H3SiC1, €12SiC12, and HSiC13, whereas with 3-picoline the two hypervalent silicon compounds H2SiC12-( 3 ~i c ) ~ and [H2Si(3pic)4]C12 . 4 CHC13 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]C12. 4 CHC1, 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(3pi~)4]2-and two C1-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 IH'H ROESY experiment suggest that dissolution has no significant impact on the molecular structure of (H,Si(3pic)4]C12 . 4 CHC13.