Reactivity of the disilyne RSiSiR (R = SiiPr[CH(SiMe3)2]2) toward bis(silylcyanide) forming a 1,4‐diaza‐2,3‐disilabenzene analog

The reaction of 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyl-2-tetrasilyne 1 with 1,3-bis(cyanodimethylsilyl)propane 4 produced the 1:1 adduct, 1,4-diaza-2,3-disilabenzene analog 5 as deep red crystals, which was characterized by spectroscopic data and X-ray crystallography. Theoretical calculations on the reaction between the disilyne and silylcyanide show that the reaction proceeds via σ-coordination of silylcyanide, in which two molecules of silylcyanide coordinate with the sp-silicon atoms of disilyne, enabling CC bond formation. Copyright © 2009 John Wiley & Sons, Ltd.