Klapötke Thomas M, Krumm Burkhard, Scherr Matthias
Department of Chemistry and Biochemistry, Ludwig-Maximilian University of Munich, Munich, Germany.
Inorg Chem. 2008 Jun 2;47(11):4712-22. doi: 10.1021/ic800051s. Epub 2008 Apr 29.
The reaction of organoselenides and -diselenides (R2Se and (RSe)2) with XeF2 furnished the corresponding organoselenium(IV) difluorides R2SeF2 (R=Me (1), Et (2), iPr (3), Ph (4), Mes (=2,4,6-(Me)3C6H2) (5), Tipp (=2,4,6-(iPr)3C6H2) (6), 2-Me 2NCH2C6H4 (7)), and trifluorides RSeF3 (R=Me (8), iPr (9), Ph (10), Mes (11), Tipp (12), Mes* (=2,4,6-(tBu) 3C6H2) (13), 2-Me2NCH2C6H4 (14)), respectively. In addition to characterization by multinuclear NMR spectroscopy, the first molecular structure of an organoselenium(IV) difluoride as well as the molecular structures of subsequent decomposition products have been determined. The substitution of fluorine atoms with Me3SiN3 leads to the corresponding organoselenium(IV) diazides R2Se(N3)2 (R=Me (15), Et (16), iPr (17), Ph (18), Mes (19), 2-Me 2NCH2C6H4 (20)) and triazides RSe(N3)3 (R=Me (21), iPr (22), Ph (23), Mes (24), Tipp (25), Mes* (26), 2-Me2NCH2C6H4 (27)), respectively. The organoselenium azides are extremely temperature-sensitive materials and can only be handled at low temperatures.
有机硒化物和二硒化物（R2Se和(RSe)2）与XeF2反应分别生成相应的有机硒(IV)二氟化物R2SeF2（R = 甲基 (1)、乙基 (2)、异丙基 (3)、苯基 (4)、均三甲苯基(=2,4,6-(甲基)3C6H2) (5)、三异丙基苯基(=2,4,6-(异丙基)3C6H2) (6)、2-甲基-2-氨基甲基苯 (7)）和三氟化物RSeF3（R = 甲基 (8)、异丙基 (9)、苯基 (10)、均三甲苯基 (11)、三异丙基苯基 (12)、特丁基均三甲苯基(=2,4,6-(叔丁基)3C6H2) (13)、2-甲基-2-氨基甲基苯 (14)）。除了通过多核核磁共振光谱进行表征外，还测定了一种有机硒(IV)二氟化物的首个分子结构以及后续分解产物的分子结构。用Me3SiN3取代氟原子分别生成相应的有机硒(IV)二叠氮化物R2Se(N3)2（R = 甲基 (15)、乙基 (１６)、异丙基 (17)、苯基 (18)、均三甲苯基 (19)、2-甲基-2-氨基甲基苯 (20)）和三叠氮化物RSe(N3)3（R = 甲基 (21)、异丙基 (22)、苯基 (23)、均三甲苯基 (24)、三异丙基苯基 (25)、特丁基均三甲苯基 (26)、2-甲基-2-氨基甲基苯 (27)）。有机硒叠氮化物是对温度极其敏感的物质，只能在低温下处理。
