連二次硝酸鹽
連二次硝酸鹽是含有連二次硝酸根N
2O2−
2（[ON=NO]2−）的化合物，而相關的連二次硝酸酯則是結構為R1−O−N=N−O−R2的化合物，其中R1和R2都是有機基團。[1]它們可看作是連二次硝酸H
2N
2O
2形成的鹽和酯。
| 連二次硝酸根 | |||
|---|---|---|---|
| |||
| IUPAC名 Hyponitrite | |||
| 系統名 Diazenebis(olate) | |||
| 別名 | 連二亞硝酸根 | ||
| 識別 | |||
| CAS號 | |||
| PubChem | 4686309 6185901（反式） | ||
| ChemSpider | 3874228 | ||
| SMILES |
| ||
| InChI |
| ||
| InChIKey | NFMHSPWHNQRFNR-UHFFFAOYSA-L | ||
| Gmelin | 130273 | ||
| 3DMet | B00354 | ||
| ChEBI | 18210 | ||
| KEGG | C01818 | ||
| 性質 | |||
| 化學式 | N 2O2− 2 | ||
| 摩爾質量 | 60.01 g·mol⁻¹ | ||
| 相關物質 | |||
| 相關氮的含氧酸鹽 | 硝酸鹽 NO− 3 亞硝酸鹽 NO− 2 過氧亞硝酸鹽 OONO− 過氧硝酸鹽 HNO− 4 原硝酸鹽 NO3− 4 | ||
| 若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。 | |||
連二次硝酸根
連二次硝酸根有順反異構。[2]諸如連二次硝酸鈉（Na
2N
2O
2）和連二次硝酸銀（Ag
2N
2O
2）的連二次硝酸鹽中的連二次硝酸根通常呈反式結構。
順式連二次硝酸根比反式連二次硝酸根活潑，存在於順式連二次硝酸鈉中。[2]它幾乎是平的，N−O鍵長140 pm、N−N鍵長120 pm、O−N−N鍵角119°。[3]
連二次硝酸酯
連二次硝酸酯R1−O−N=N−O−R2可由連二次硝酸銀Ag
2N
2O
2和鹵代烴反應產生，例如和叔丁基氯反應產生連二次硝酸二叔丁酯。[4][5][6][7]除此之外，連二次硝酸還可以形成二乙酯、二丙酯、二丁酯[8]和二苄酯。[9][10][11]它們可以產生烷氧基自由基。[12]
製備
連二次硝酸鈉的順式異構體可由氧化鈉和一氧化二氮在高溫下反應而成，[13]而反式異構體則通過亞硝酸鈉水溶液與鈉汞齊的反應產生。[14][15]其它連二次硝酸鹽可以以連二次硝酸鈉為原料製備。[16]
反應
連二次硝酸根是雙齒配體，紅色的[(NH3)5Co(μ-N2O2)Co(NH3)5]4+就是一例。[15][16]連二次硝酸鹽對還原劑穩定，但在某些條件下會變成還原劑，如和碘的反應：[15]
- N
2O2−
2 + 3 I
2 + 3 H
2O → NO−
3 + NO−
2 + 6 HI
連二次硝酸鹽和液態四氧化二氮的反應緩慢，但如果反應在硝基甲烷里發生，那麼反應會變得迅速：[15]
- [O−N=N−O]2− + 2 N
2O
4 → 2 NO−
3 + [ONON=NONO] - [ONON=NONO] → N
2 + 2 NO
2
參考資料
- ^ Hughes, M. N. Hyponitrites. Quarterly Reviews, Chemical Society (Royal Society of Chemistry (RSC)). 1968, 22 (1): 1. ISSN 0009-2681. doi:10.1039/qr9682200001.
- ^ 2.0 2.1 Wiberg, Egon; Holleman, A. F.; Wiberg, Nils. Inorganic Chemistry. Academic Press. 2001. ISBN 0-12-352651-5.
- ^ Feldmann, Claus; Jansen, Martin. cis-Sodium Hyponitrite—A New Preparative Route and a Crystal Structure Analysis. Angewandte Chemie International Edition in English (Wiley). 1996, 35 (15): 1728–1730. ISSN 0570-0833. doi:10.1002/anie.199617281.
- ^ Navamoney Arulsamy; D. Scott Bohle; Jerome A. Imonigie; Elizabeth S. Sagan. Correlation of the Product E/Z Framework Geometry and O/O vs O/N Regioselectivity in the Dialkylation of Hyponitrite. J. Am. Chem. Soc. 2000, 122 (23): 5539–5549. doi:10.1021/ja994261o.
- ^ Kiefer, Hansruedi; Traylor, T.G. Di-t-butyl hyponitrite. A convenient source of t-butoxy radicals. Tetrahedron Letters (Elsevier BV). 1966, 7 (49): 6163–6168. ISSN 0040-4039. doi:10.1016/s0040-4039(00)70159-6.
- ^ Huang, R. L.; Lee, Tong-Wai; Ong, S. H. Reactions of the α-methoxybenzyl radical in carbon tetrachloride and in other solvents. Carbon tetrachloride as a chlorinating agent. J. Chem. Soc. C (Royal Society of Chemistry (RSC)). 1969, 0 (1): 40–44. ISSN 0022-4952. doi:10.1039/j39690000040.
- ^ Neuman, Robert C.; Bussey, Robert J. High pressure studies. V. Activation volumes for combination and diffusion of geminate tert-butoxy radicals. Journal of the American Chemical Society (American Chemical Society (ACS)). 1970, 92 (8): 2440–2445. ISSN 0002-7863. doi:10.1021/ja00711a039.
- ^ Partington, James R.; Shah, Chandulal C. 384. Hyponitrites. Part II : metallic salts. Part III : esters. Journal of the Chemical Society (Resumed) (Royal Society of Chemistry (RSC)). 1932: 2589. ISSN 0368-1769. doi:10.1039/jr9320002589.
- ^ Ho, S. K.; de Sousa, J. B. 347. Alkoxy-radicals. Part I. The kinetics of thermal decomposition of dibenzyl hyponitrite in solution. Journal of the Chemical Society (Resumed) (Royal Society of Chemistry (RSC)). 1961: 1788. ISSN 0368-1769. doi:10.1039/jr9610001788.
- ^ de SOUSA, J. B.; HO, S. K. Disproportionation and Dimerization of the Benzyloxyl Free Radical in Solution. Nature (Springer Science and Business Media LLC). 1960, 186 (4727): 776–778. ISSN 0028-0836. doi:10.1038/186776a0.
- ^ Ray, N. H. 794. The rates of decomposition of free-radical polymerisation-catalysts: measurements of short half-lives by a thermal method. Journal of the Chemical Society (Resumed) (Royal Society of Chemistry (RSC)). 1960: 4023. ISSN 0368-1769. doi:10.1039/jr9600004023.
- ^ Craig A. Ogle; Steven W. Martin; Michael P. Dziobak; Marek W. Urban; G. David Mendenhall. Decomposition rates, synthesis, and spectral properties of a series of alkyl hyponitrites. J. Org. Chem. 1983, 48 (21): 3728–3733. doi:10.1021/jo00169a023.
- ^ Feldmann, Claus; Jansen, Martin. cis-Sodium Hyponitrite—A New Preparative Route and a Crystal Structure Analysis. Angewandte Chemie International Edition in English (Wiley). 1996, 35 (15): 1728–1730. ISSN 0570-0833. doi:10.1002/anie.199617281.
- ^ Addison, C. C.; Gamlen G. A.; Thompson, R. 70. The ultra-violet absorption spectra of sodium hyponitrite and sodium α-oxyhyponitrite : the analysis of mixtures with sodium nitrite and nitrate. J. Chem. Soc. 1952: 338–345. doi:10.1039/jr9520000338.
- ^ 15.0 15.1 15.2 15.3 Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997. ISBN 0-7506-3365-4.
- ^ 16.0 16.1 Awasabisah, Dennis; Richter-Addo, George B. NOx Linkage Isomerization in Metal Complexes. NOx Related Chemistry. Elsevier. 2015. ISSN 0898-8838. doi:10.1016/bs.adioch.2014.11.003.