Hydrazines transition metal complexes

Numerous explosives are based on hydrazine and its derivatives, including the simple azide, nitrate, perchlorate, and diperchlorate salts. These are sometimes dissolved in anhydrous hydrazine for propeUant appUcations or in mixtures with other explosives (207). Hydrazine transition-metal complexes of nitrates, azides, and perchlorates are primary explosives (208). 

Studies on model polynuclear catalytic systems have confirmed that for the catalytic reduction of dinitrogen under mild conditions, it is necessary to use a polynuclear transition metal complex capable of donating four electrons to form the hydrazine derivative. 

An example of a substituted hydrazine (1-) complex is Ge[N(Me)NMe2]4 which has a distorted tetrahedral structure complexes of other main group elements (as well as transition metal complexes) are known.179 An example of a NHNH2 species is Cp Me4W(T72-NHNH2).180... 

The reactions of hydrazine with 22 transition-metal complexes (132)... 

Zeolite-supported transition metal complexes, such as Mn(III) porphyrin and Cu(II) tetraphenylporphyrin, have been used for the electrocatalytic oxidation of phenols and hydrazine, respectively [173]. Methylviologen-exchanged zeolites have... 

Transition metal complexes containing monodentate and bridging hydrazines are well known. The complexes of transition metal salts of divalent metals like Co " " and Ni + with anions such as Cl , N02, NOs , S04 , C103, and C104, with 1,2, or 3 coordinated molecules... 

Bottomley, F. (1970) The reactions of hydrazine with transition-metal complexes. Quarterly Reviews, Chemical Society, 24, 617-638. 

One of the most dramatic developments in the chemistry of N2 during the past 30 years was the discovery by A. D. Allen and C. V. Senoff in 1965 that dinitrogen complexes such as [Ru(NH3)5(N2)1 could readily be prepared from aqueous RUCI3 using hydrazine hydrate in aqueous solution. Since that time virtually all transition metals have been found to give dinitrogen complexes and several hundred such compounds are now characterized.Three general preparative methods are available ... 

The reduction of silver(I) ions by hydrazine was characterized by a long induction period where a 1 1 complex formed (log Ki 3.2).117 The nature of the complex was not established. Several hydrazinates of silver have been identified and the preparation of Ag2S04-3N2H4 was reported in 1932.116 The rate of the reduction to metallic silver was found to be influenced by pH and composition of the solution phase. Hydrazine complexes of transition metal ions in general have been reviewed.118,119... 

Thiosemicarbazides (TSC) and thiosemicarbazones generally react with transition metal ions to form chelate complexes by bonding through both the sulfur and the hydrazinic nitrogen atoms. With silver(I) however, they appear to behave as monodentate ligands and bond through the sulfur atom only.436... 

The reaction of phenylhydrazine with copper(II) chloride in aqueous solution gives [Cu4Cl4(PhNNH)] (13) and the reactions of 1,2-disubsti-tuted hydrazines with copper(II) salts give complexes such as [Cu2-Cl2(MeNNMe)l (46, 142). The reaction of substituted hydrazines (or lithiated, substituted hydrazines) with halido complexes of the transition metals can yield diazene complexes. Complexes of Ni, Pd, Pt (147, 199,213), and Rh (209) have been prepared in this manner [Eq. (25)]. 

Organic derivatives of tetrazane ( buzane ) H2N—NH—NH—NH2 have been known since 1893 (227), but to date no transition metal tetrazane complexes have been fully characterized. However, iron tetrazane species have been proposed as intermediates in the iron(II)-catalyzed aerobic oxidation of hydrazines (104,230) and are thought to account for the red coloration observed in some of these reactions (230). 

Tetrazane complexes may form as unstable intermediates during the transition metal catalyzed oxidation of hydrazines. Tetrazene adducts are... 

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