Pentafluorosulfanylnitramide Salts
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- 作者：Michael E. Sitzmann ; Richard Gilardi ; Ray J. Butcher ; William M. Koppes ; Alfred G. Stern ; Joseph S. Thrasher ; Nirupam J. Trivedi ; and Zhen-Yu Yang
- 刊名：Inorganic Chemistry
- 出版年：2000
- 出版时间：February 21, 2000
- 年：2000
- 卷：39
- 期：4
- 页码：843 - 850
- 全文大小：141K
- 年卷期：v.39,no.4(February 21, 2000)
- ISSN：1520-510X
文摘
The synthesis and properties of a new class of inorganic salts, named pentafluorosulfanylnitramide salts (orpentafluorosulfanylnitraminic acid salts) [Z+SF5NNO2-], are described. A number of SF5-nitramide salts(Z+SF5NNO2-) were successfully prepared via nucleophilic displacements from carbamates and/or ion exchangetechniques, but some salts [M(SF5NNO2)x; M = Li, Mg, Al] decomposed during isolation procedures and appearto be unstable in the solid state. Single-crystal X-ray diffraction was used to fully characterize the Z+SF5NNO2-,and their properties/structures are compared with those of the corresponding dinitramide salts (or dinitraminicacid salts), Z+N(NO2)2-. X-ray crystallography revealed major structural differences between N(NO2)2- andSF5N(NO2)- salts concerning the N-N distances and the angles subtended at the central nitrogen atom. In theN(NO2)2- salts, there are two nonequivalent N-N (average lengths 1.372(2) and 1.354(2) Å) distances and anaverage N-N-N angle of 115.8(3)
(falls between sp3 and sp2 hybridization). In the SF5NNO2- salts, the averageN-N distance is much shorter, 1.308(9) Å, and the average N-N-S angle is 120.0(5) (closely fits sp2hybridization). The SF5NNO2- salts show a remarkable metrical similarity for the SF5 moiety in all structures,indicating a lack of sensitivity to its steric and electronic environment. This is in marked contrast to N(NO2)2-,where there is a wide variation in conformations adopted by these anions which can be related to their environment.
(falls between sp3 and sp2 hybridization). In the SF5NNO2- salts, the averageN-N distance is much shorter, 1.308(9) Å, and the average N-N-S angle is 120.0(5) (closely fits sp2hybridization). The SF5NNO2- salts show a remarkable metrical similarity for the SF5 moiety in all structures,indicating a lack of sensitivity to its steric and electronic environment. This is in marked contrast to N(NO2)2-,where there is a wide variation in conformations adopted by these anions which can be related to their environment.