Abstract
Syntheses, structures, thermolyses of pentacoordinate 1,2-oxasiletanides ( 1), K +, 18-crown-6, {[C 6H 4C(CF 3) 2O]SiPh[CHRCR 1R 2O]} −, pentacoordinate1,2-oxastannetanides ( 2), K +, 18-crown-6, {Ph 3Sn[CH(SPh)CR 1R 2O]} −, pentacoordinate 1,2-oxagermetanide ( 3), K +, 18-crown-6, {[C 6H 4C(CF 3) 2O]GePh[CH(CH 2- t-Bu)C(CF 3) 2O]} −, germylalkoxide ( 4), K +, 18-crown-6, Ph 3GeCH(CH 2- t-Bu)C(CF 3) 2O −, pentacoordinate siprobi[1,2-oxasiletanide] ( 5), DBU·H +, {PhSi[-CH 2C(CF 3) 2O] 2} − are summarized. All compounds except for spirobi[1,2-oxasiletanide] 5, which underwent homo-Brook rearrangement, gave the corresponding olefins upon heating, indicating that they are intermediates of Peterson-type reactions. However, it was found that 1,2-oxasiletanides bearing the Martin ligand, which usually undergo the Peterson reaction, can afford the homo-Brook rearrangement products depending on the substituent at the 3-position and the reaction conditions, demonstrating that the Peterson reaction and homo-Brook rearrangement proceed via a common intermediate, a pentacoordinate 1,2-oxasiletanide. Crystal structures of these compounds are also presented.
Published Version
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