肼錯合物
外觀
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肼錯合物又稱聯氨錯合物,是指金屬和肼(N2H4)形成的配位化合物。肼錯合物可用作製備一些無機材料的前驅體,或者直接作為含能材料。[1]
![](http://upload.wikimedia.org/wikipedia/commons/thumb/b/be/Bridged_bidentate_hydrazine.png/220px-Bridged_bidentate_hydrazine.png)
製備
[編輯]肼錯合物可以通過金屬鹽和肼在水溶液中直接反應得到:[1]
- M(NO3)2~3 + 3 N2H4 → [M(N2H4)3](NO3)2~3 (M=Co, Ni, Zn, Cd, Cr)
在反應中,原先錯合物中配位能力比肼弱的配位基可能會被取代,例如:[2]
- M(CO)2(PPh3)2X(OSO2CF3) + N2H4 → [M(CO)2(PPh3)2(N2H4)X](OSO2CF3) (M=Ru, X=Cl 或 M=Os, X=Br)
其它製備方法還包括金屬和含有肼的銨鹽溶液反應、金屬直接與𨥙鹽反應等。[3]
性質
[編輯]肼在錯合物中可以以單齒配位基、雙齒配位基或者橋聯配位基與金屬連接。[2]肼錯合物的其它一些性質參見下表。
化學式 | 名稱 | 結構性質 | 理化性質 | 參考文獻 |
---|---|---|---|---|
Mg(N3)2(N2H4)2 | 疊氮化二肼合鎂 | IR (cm−1): N3 1310 (sym.), 2080 (asym.) | 125 °C開始第一階段分解,得到Mg(N2)(NH2)2,217 °C開始第二階段分解,得到MgNH | Patil |
Ba(N2H3COO)2(N2H4)2 | 二肼合肼基甲酸鋇 | 單斜晶系,空間群C2,d (Å) N-N: 1.43, 1.41 | Patil | |
[Cr(N2H4)3](NO3)3 | 硝酸三肼合鉻(III) | IR (KBr, cm−1): NH2 1628, 3234; NO3 1362 | FS 64, IS >25, SES 1.167 | Wojewódka |
[Cr(N2H4)3](ClO4)3 | 過氯酸三肼合鉻(III) | IR (KBr, cm−1): NH2 1628, 3245; ClO4 1092 | FS 96, IS 2, SES 1.750 | Wojewódka |
Mn(N2H4)2Cl2 | 氯化二肼合錳(II) | 單斜晶系,空間群C2/m,d (Å) N-N: 1.459 | Patil | |
Mn(NCS)2(N2H4)2 | 二肼合異硫氰酸錳(II) | 磁矩 5.87 BM(23 °C) | 白色固體,加熱分解為Mn(NCS)2,並放出NH3和N2 | Patil |
Mn(CH3COO)2(N2H4)2 | 二肼合乙酸錳(II) | IR (cm−1): COO 1420(sym.), 1610(asym.) | 130 °C開始分解,經Mn(CH3COO)2·1/2N2H4和Mn(CH3COO)2,最終得到MnO2 | [4] |
Fe(NCS)2(N2H4)2 | 二肼合異硫氰酸鐵(II) | 磁矩 4.91 BM(23 °C) | 白色固體,加熱分解為Fe(NCS)(CN) | Patil |
[Co(N2H4)3](NO3)2 | 硝酸三肼合鈷(II) | IR (KBr, cm−1): NH2 1624, 3265; NO3 1381 | FS 60, IS >25, SES 2.250 | Wojewódka |
[Co(N2H4)3](ClO4)2 | 過氯酸三肼合鈷(II) | IR (KBr, cm−1): NH2 1628, 3241; ClO4 1142 | FS 36, IS >25, SES 0.840 | Wojewódka |
Co(NCS)2(N2H4)2 | 二肼合異硫氰酸鈷(II) | 磁矩 4.80 BM(23 °C) | 粉色固體,加熱分解為Co(NCS)(CN) | Patil |
Co(C3H2O4)(N2H4)2 | 二肼合丙二酸鈷(II) | 結構中N2H4為橋聯配位基 | 玫瑰紅色固體 | Sivasankar |
Co(C4H4O4)(N2H4)2 | 二肼合丁二酸鈷(II) | 結構中N2H4為橋聯配位基 | 玫瑰紅色固體 | Sivasankar |
Co3(C6H5O7)2·6N2H4 | 六肼合檸檬酸鈷 | 磁矩4.90 BM | 粉色固體,熱分解產物Co3O4 | Yasodhai |
[Ni(N2H4)3](NO3)2 | 硝酸三肼合鎳 | IR (KBr, cm−1): NH2 1628, 3241; NO3 1385 | FS 24, IS 10, SES 0.027 對水穩定;可以和10%氫氧化鈉溶液溫和地反應;遇濃硫酸起火 |
Wojewódka [5] |
NiSO4·3N2H4 | 三肼合硫酸鎳 | 分解為硫酸鹽的反應熱:452 cal/g | 265 °C分解為NiSO4 | [6] |
Ni(NCS)2(N2H4)2 | 二肼合異硫氰酸鎳 | 磁矩 2.82 BM(23 °C) | 藍色固體,加熱分解為Ni(NCS)(CN) | Patil |
Ni(C3H2O4)(N2H4)2 | 二肼合丙二酸鎳 | 結構中N2H4為橋聯配位基 | 淺紫色固體 | Sivasankar |
Ni(C4H4O4)(N2H4)2 | 二肼合丁二酸鎳 | 結構中N2H4為橋聯配位基 | 淺紫色固體 | Sivasankar |
Ni3(C6H5O7)2·6N2H4 | 六肼合檸檬酸鎳 | 磁矩3.20 BM | 藍紫色固體,熱分解產物NiO | Yasodhai |
[Cu(N2H4)]Cl | 氯化一肼合銅(I) | 結構中N2H4為橋聯配位基;分子有反磁性 | 白色固體,在空氣中迅速氧化為二價銅 | [7] |
{Cu(μ2-CN)(μ2-N2H4)}n | 氰化一肼合銅(I) | 正交晶系,空間群Pbcm d (Å) Cu-N 2.17(1), N-N 1.48(2), Cu-N-N (°) 114.2(7) |
[8] | |
CuC2O4·2N2H4 | 二肼合草酸銅(II) | IR (cm−1): COO 1370 (sym.), 1660 (asym.) | 不穩定。在空氣中失去一分子N2H4,變為穩定的CuC2O4·N2H4。152 °C分解為CuC2O4 | Patil |
Cu2C6H4O7·N2H4·2H2O | 二水·一肼合檸檬酸二銅(II) | 磁矩1.80 BM | 深藍色固體,熱分解產物CuO | Yasodhai |
[Zn(N2H4)3](NO3)2 | 硝酸三肼合鋅 | IR (KBr, cm−1): NH2 1624, 3261; NO3 1381 | FS >360, IS >25, SES 0.720 | Wojewódka |
[Zn(N2H4)3](ClO4)2 | 過氯酸三肼合鋅 | IR (KBr, cm−1): NH2 1609, 3241; ClO4 1084 | FS 192, IS >25, SES 9.000 | Wojewódka |
Zn(C3H2O4)(N2H4)2 | 二肼合丙二酸鋅 | 結構中N2H4為橋聯配位基 | 無色固體 | Sivasankar |
Zn(C4H4O4)(N2H4)2 | 二肼合丁二酸鋅 | 結構中N2H4為橋聯配位基 | 無色固體 | Sivasankar |
Zn3(C6H5O7)2·6N2H4 | 六肼合檸檬酸鋅 | 反磁性 | 無色固體,熱分解產物ZnO | Yasodhai |
[Cd(N2H4)3](NO3)2 | 硝酸三肼合鎘 | IR (KBr, cm−1): NH2 1597, 3265; NO3 1354 | FS 216, IS >25, SES 0.080 | Wojewódka |
[Cd(N2H4)3](ClO4)2 | 過氯酸三肼合鎘 | IR (KBr, cm−1): NH2 1605, 3245; ClO4 1084 | FS 2, IS 6, SES 0.010 | Wojewódka |
Cd(C3H2O4)(N2H4)2 | 二肼合丙二酸鎘 | 結構中N2H4為橋聯配位基 | 無色固體 | Sivasankar |
Cd(C4H4O4)(N2H4)2 | 二肼合丁二酸鎘 | 結構中N2H4為橋聯配位基 | 無色固體 | Sivasankar |
Cd3(C6H5O7)2·6N2H4 | 六肼合檸檬酸鎘 | 反磁性 | 無色固體,熱分解產物CdO | Yasodhai |
Ce(SO4)2·2N2H4 | 二肼合硫酸鈰(IV) | 分解為硫酸鹽的反應熱:65 cal/g | 275 °C分解為Ce(SO4)2 | Athavale |
UO2SO4·2N2H4 | 二肼合硫酸鈾醯 | 分解為硫酸鹽的反應熱:173 cal/g | 185 °C分解為UO2SO4 | Athavale |
Th(SO4)2·2N2H4 | 二肼合硫酸釷 | 分解為硫酸鹽的反應熱:75 cal/g | 265 °C分解為Th(SO4)2 | Athavale |
註:參考文獻中人名對應的文獻是:Wojewódka[1]、Athavale[6]、Sivasankar[9]、Yasodhai[10]、Patil[11]。表中使用的縮寫:IR 紅外;FS 摩擦感度(N),IS 撞擊感度(Nm),SES 靜電感度(J);d 鍵長。
應用
[編輯]肼錯合物可以用於製備一些無機材料,如氧化物[3]、金屬[12]等。還有一些肼錯合物可以直接用作含能材料。[5]一些肼錯合物也可用作火箭燃料。
安全
[編輯]合成肼錯合物時可能用到高毒的肼,應當注意防護。[13]肼的一些錯合物是易爆危險品,應當按照規範操作。[14]
參考文獻
[編輯]- ^ 1.0 1.1 1.2 Wojewódka A, Bełzowski J. Hydrazine Complexes of Transition Metals as Prospective Explosives. Chemik, 2011, 65(1): 24-27.
- ^ 2.0 2.1 Heaton, Brian T.; Jacob, Chacko; Page, Philip. Transition metal complexes containing hydrazine and substituted hydrazines. Coordination Chemistry Reviews. 1996, 154: 193–229. ISSN 0010-8545. doi:10.1016/0010-8545(96)01285-4.
- ^ 3.0 3.1 Patil, K C. Metal-hydrazine complexes as precursors to oxide materials. Journal of Chemical Sciences. 1986, 96 (6): 459–464. ISSN 0253-4134. doi:10.1007/BF02936298.
- ^ Mahesh, G.V.; Patil, K.C. Thermal reactivity of metal acetate hydrazinates. Thermochimica Acta. 1986, 99: 153–158. ISSN 0040-6031. doi:10.1016/0040-6031(86)85277-7.
- ^ 5.0 5.1 Shunguan, Zhu; Youchen, Wu; Wenyi, Zhang; Jingyan, Mu. Evaluation of a New Primary Explosive: Nickel Hydrazine Nitrate (NHN) complex. Propellants, Explosives, Pyrotechnics. 1997, 22 (6): 317–320. ISSN 0721-3115. doi:10.1002/prep.19970220604.
- ^ 6.0 6.1 Athavale, V.T.; Padmanabha Iyer, C.S. Studies on some metal-hydrazine complexes. Journal of Inorganic and Nuclear Chemistry. 1967, 29 (4): 1003–1012. ISSN 0022-1902. doi:10.1016/0022-1902(67)80085-X.
- ^ Brown, David B.; Donner, Jeffrey A.; Hall, James W.; Wilson, Scott R.; Wilson, Roxy B.; Hodgson, Derek J.; Hatfield, William E. Interaction of hydrazine with copper(II) chloride in acidic solutions. Formation, spectral and magnetic properties, and structures of copper(II), copper(I), and mixed-valence species. Inorganic Chemistry. 2002, 18 (10): 2635–2641. ISSN 0020-1669. doi:10.1021/ic50200a001.
- ^ Cromer, D. T.; Larson, A. C.; Roof, R. B. The crystal structure of copper(I) cyanide hydrazine complex, CuCN.N2H4. Acta Crystallographica. 1966, 20 (2): 279–282. ISSN 0365-110X. doi:10.1107/S0365110X66000537.
- ^ Sivasankar, B. N.; Govindarajan, S. Studies on bis(Hydrazine) Metal Malonates and Succinates. Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry. 1994, 24 (9): 1573–1582. ISSN 0094-5714. doi:10.1080/00945719408002581.
- ^ Yasodhai, S.; Sivakumar, T.; Govindarajan, S. Preparation, characterisation and thermal reactivity of transition metal complexes of hydrazine with citric acid. Thermochimica Acta. 1999, 338 (1-2): 57–65. ISSN 0040-6031. doi:10.1016/S0040-6031(99)00192-6.
- ^ K. C. Patil. Inorganic Hydrazine Derivatives - Synthesis, Properties and Applications. Wiley, 2014. ISBN 9781118715130
- ^ Park, Jung Woo; Chae, Eun H.; Kim, Sang H.; Lee, Jong Ho; Kim, Jeong Wook; Yoon, Seon Mi; Choi, Jae-Young. Preparation of fine Ni powders from nickel hydrazine complex. Materials Chemistry and Physics. 2006, 97 (2-3): 371–378. ISSN 0254-0584. doi:10.1016/j.matchemphys.2005.08.028.
- ^ Occupational Safety and Health Guideline for Hydrazine—Potential Human Carcinogen (PDF). NIOSH. 1988 [23 Nov 2018]. (原始內容 (PDF)存檔於2021-03-22).
- ^ Talawar, M B; Agrawal, A P; Chhabra, J S; Ghatak, C K; Asthana, S N; Rao, K U B. Studies on nickel hydrazinium nitrate (NHN) and bis-(5-nitro-2H tetrazolato-N2)tetraamino cobalt(III) perchlorate (BNCP): Potential lead-free advanced primary explosives (頁面存檔備份,存於網際網路檔案館). CSIR, 2004. 677-681. ISSN: 0975-1084.
拓展閱讀
[編輯]
- Bottomley, F. The reactions of hydrazine with transition-metal complexes. Quarterly Reviews, Chemical Society. 1970, 24 (4): 617. ISSN 0009-2681. doi:10.1039/qr9702400617.
- Sacconi, L.; Sabatini, A. The infra-red spectra of metal(II)-hydrazine complexes. Journal of Inorganic and Nuclear Chemistry. 1963, 25 (11): 1389–1393. ISSN 0022-1902. doi:10.1016/0022-1902(63)80408-X.
- Dilworth, J.R. The coordination chemistry of substituted hydrazines. Coordination Chemistry Reviews. 1976, 21 (1): 29–62. ISSN 0010-8545. doi:10.1016/S0010-8545(00)82050-0.
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