Diverse reactions of nitroxide-radical adducts of silylene, germylene, and stannylene

A Radical Approach to Hydroxylaminotrichlorosilanes: Synthesis, Reactivity, and Crystal Structure of TEMPO‐SiCl3 (TEMPO = 2,2,6,6‐Tetramethylpiperidine‐N‐oxyl)

“…[10] Although we found that TEMPO is a good alternative to other known relaxation enhancers in 29 Si NMR spectroscopy, we also realized that very sensitive compounds may react with TEMPO. For organosilicon compounds, it is known from literature that silylenes [11][12][13][14] and H-silanes [2,3,5,6] are oxidized in the presence of TEMPO under certain conditions. It is also known that hypervalent silicon-porphyrin complexes can react with TEMPO upon irradiation with UV light.…”

Recent developments in the chemistry of stable silylenes

“…In contrast, the 1:1 germoxy and stannoxy radical adducts simply couple with a further molecule of TEMPO to give the observed 1:2 adducts 21. DFT calculations indicate that O-N bond cleavage is slightly exothermic in the siloxyl radical but strongly endothermic for the corresponding germanium and tin species [40]. Stable 1:2 adducts were obtained from the reaction of TEMPO with the germanium analogs of 1 and 2 [38].…”

Theoretical prediction on the addition reaction of germylenoid H2GeFMgF with ethylene

“…[1][2][3][4][5] The reactions of germylenes such as insertion, 6,7 addition 8-10 and polymerization, 11 are recognized as important and e®ective methods for the preparation of new germanium-bonded and heterocyclic germanium compounds. The formation of highly strained small ring molecules using -type additions of germylenes to multiple bonds has also been an important topic in the area of germylene chemistry.…”