Reactions of Silicon Atoms with Cyanogen: Generation and Matrix‐Spectroscopic Identification of Five C₂N₂Si Isomers

Abstract

The reactions of silicon atoms with cyanogen 12 in an argon matrix at 10 K have been studied. In the initial step a triplet n adduct T‐13 is formed between a silicon atom and 12. The next step needs photochemical activation. Long‐wavelength irradiation yields 3‐cyanoazasilacyclopropenylidene 14, which upon irradiation with 254 nm light is transformed into three isomeric silylenes: dicyanosilylene 15, cyano(isocyano)silylene 16, and di(isocyano)silylene 17. The structural elucidation of all new species is based on comparison of the experimentally obtained IR and UV/Vis spectra with the results of density functional theory calculations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Dicyanogermylenes: A Tale of Isomers and Interconversions

“…Maier and Reisenauer 42 calculated the geometries and relative energies of C 3 N 2 isomers in their singlet and triplet states, and the global minimum was located as triplet linear C(CN) 2 (D ∞h , 3 Σ g − ). Maier et al 43 also studied five C 2 N 2 Si isomers pertinent to the reaction Si ( 3 P) + NC−CN (D ∞h , 1 Σ g ), identifying the bent Si(NC) 2 as the global minimum and the next two higher isomers as NCSiNC and Si(CN) 2 . There are two cyclic silylenes, but the mechanism for the reorganization of the Si atom and two CN fragments is not known.…”