肼配合物

肼配合物又称联氨配合物，是指金属和肼（N2H4）形成的配位化合物。肼配合物可用作制备一些无机材料的前驱体，或者直接作为含能材料。 肼配合物可以通过金属盐和肼在水溶液中直接反应得到： M(NO3)2~3 + 3 N2H4 → [M(N2H4)3](NO3)2~3 （M=Co, Ni, Zn, Cd, Cr） 在反应中，原先配合物中配位能力比肼弱的配体可能会被取代，例如： M(CO)2(PPh3)2X(OSO2CF3) + N2H4 → [M(CO)2(PPh3)2(N2H4)X](OSO2CF3) （M=Ru, X=Cl 或 M=Os, X=Br） 其它制备方法还包括金属和含有肼的铵盐溶液反应、金属直接与𨥙鹽反应等。 肼在配合物中可以以单齿配体、双齿配体或者桥联配体与金属连接。肼配合物的其它一些性质参见下表。 注：参考文献中人名对应的文献是：Wojewódka、Athavale、Sivasankar、Yasodhai、Patil。表中使用的缩写：IR 红外；FS 摩擦感度（N），IS 撞击感度（Nm），SES 静电感度（J）；d 键长。 肼配合物可以用于制备一些无机材料，如氧化物、金属等。还有一些肼配合物可以直接用作含能材料。一些肼配合物也可用作火箭燃料。 合成肼配合物时可能用到高毒的肼，应当注意防护。肼的一些配合物是易爆危险品，应当按照规范操作。 Wojewódka A, Bełzowski J. Hydrazine Complexes of Transition Metals as Prospective Explosives. Chemik, 2011, 65(1): 24-27. 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.  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.  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.  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]. （原始内容 (PDF)存档于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 （页面存档备份，存于互联网档案馆）. CSIR, 2004. 677-681. ISSN: 0975-1084. 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.