Generation,low-temperature stabilization,structure, and reactivity of intermediates with low-coordinated carbon,silicon, and germanium atoms

The mechanisms of thermal and photochemical transformations of organic and organometallic compounds which pass through formation of different reactive intermediates were investigated by low-temperature matrix IR spectroscopy. Low-temperature matrix stabilization of the intermediates, the primary products of these reactions, was conducted at 10–15 K. The spectral and structural parameters of the free radicals (CCl₃, CCl₂Br, CClBr₂, CH₂CH=CH₂, CF₂CF=CF₂, CH₂-CCH, CH₂CN, CH₂Ph, CF₂C₆F₅), halocarbenes and their silicon and germanium analogs, and unstable molecules with double-bond silicon and germanium atoms were obtained as a result.The article is based on a plenary report to the 10th IUPAC Conference on Physical-Organic Chemistry (Haifa, Israel, August, 1990) [1] and partially includes data from Low-Temperature Matrix Stabilization and IR Spectroscopic Study of Free Radicals by O. M. Nefedov, A. K. Mal'tsev, and V. A. Korolev, awarded the N. N. Semenov Prize, Academy of Sciences of the USSR, Moscow, for 1991.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2425–2442, November, 1991.We would like to thank V. A. Korolev for assisting in writing this article.