Diazene transition metal

Complexation and activation of diazenes and diazo compounds by transition metals. A. Albini and H. Kirsch, Top. Curr. Chem., 1976, 65,106-145 (119). 

Albini, A., and Kisch, H. Complexation and Activation of Diazenes and Diazo Compounds by Transition Metals. 65,105-145 (1976). 

Mdssbauer spectra of bonding and structure in, 15 184-187 reactions with diborane, 16 213 stabilization of, 5 17, 18-19 cyanates, 17 297, 298 cyanide complexes of, 8 143-144 cyclometallated bipyridine complex, 30 76 diazene complexes, 27 231-232 dinitrogen complexes, 27 215, 217 diphosphine complexes of, 14 208-219 dithiocarbamates, 23 253-254 -1,2-dithiolene complexes, 22 323-327 hydrogen bonding, 22 327 halide complexes with phosphine, etc., 6 25 hexaflouride, structure, 27 104 hydride complexes, 20 235, 248-281, see also Transition metal-hydride complexes... 

The redox reactions of hydrazine toward main-group and transition metal oxidants have been reviewed (73). Different stoichiometries have been found, with N2 appearing as the N-containing oxidized product, sometimes accompanied by the formation of NH3 and/or HN3. The mechanisms have been analyzed in terms of the one- or two-electron nature of the oxidants, and imply both outer-and inner-sphere routes, depending on the oxidant. The very reactive, key intermediate, diazene (diimide), N2H2, has been proposed in most of these reactions. 

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)]. 

The reaction of transition metal oxo complexes with substituted hy-drazines yields the diazene complexes, containing the M—NRNC(R)0 chelate. 

The relative instability of free diazenes (215) often precludes the direct reaction of these species with transition metal complexes. However azobenzene reacts with Ni° (264) species to yield materials such as [Ni(tBuNC)2(PhN2Ph)] (140, 265). Similarly, ditolyldiazene reacts with [Ni(cyclooctadiene)2] in the presence of tritolylphosphine to give [Ni(N2Ar2)(PAr3)2] (Ar = p-CH3C6H4) (200). 

Complexation and Activation of Diazenes and Diazo Compounds by Transition Metals... 

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