Nitrido complexes reactions

Some recent interest in the technetium chemistry has been focused on complexes possessing a Tc=N3+ core. Tetrachloronitridotechnetate(VI) complexes can easily be synthesized by the reaction of pertechnetate with sodium azide in concentrated hydrochloric acid [34], Although its square-pyramidal structure resembles that of tetrachlorooxotechnetate(V) complexes, stable character of the nitrido complexes in aqueous solution shows a remarkable contrast to the oxo complexes. However, when a strong acid and a coordinating ligand are absent, the interconversion of di(p-oxo)nitridotechnetium(VI) complexes to the monomeric form occurs in the following complicated manner [35]... 

Another example of a Tc nitrido-complex is obtained from the reaction of [TcOCU]" with 1,1-diphenylhydrazine (H2NNPh2) (23) in the presence of thiophenol. Unexpectedly, the dinuclear, formally Tc complex [ TcN(NNPh2)(SAr)(/r-SAr) 2] (24) is formed in good yields. The nitrido-group results from the cleavage of the organohydrazine. This unusual reaction is shown in Scheme 9. 

An unusual synthesis of a rhenium(VI) nitrido complex has been observed with the ligand reaction of the rhenium(V) precursor [ReNCl2(PPh3)2] with 2,4,6-tri-isopropylbenzenethiolate, tipt, which gave the green rhenium(VI) complex [ReN(tipt)4], when the reaction mixture was exposed to air, whereas the pale orange rhenium(V) compound [ReN(tipt)4] was obtained in an inert atmosphere. ... 

Whereas the oxidation state of the rhenium atom is maintained during the reaction of the potentially tetradentate ligand tris(2-diphenylphosphinoethyl)amine, NP3 (179), with the nitrido complex [ReNCl2(PPh3)2], the rhenium(III) complex [ReCl3( 7 -NPP-... 

Compared with the large number of nitrosyl complexes, only a few examples of thionitrosyl complexes have been studied. Although NS does not exist, a number of synthetic approaches to thionitrosyl complexes have been reported the reaction of nitrido complexes with S2CI2 or TMSNCS, treatment of chloro or 0x0 complexes with trithiazyl chloride or S(NTMS)2, or the use of heterocyclic nitrogen-sulfur rings. Pre-formed thionitrosyl cations in [NS][SbF6] or [NS)[AsFg] have been used to prepare the cationic complex [Re(NS)(CO)5] " in liquid S02. ... 

A ruthenium(VI) nitrido complex containing a tetrapyrrolic macrocycle ligand, [Ru (N)(L)] (82) (H4L = mcio-octamethylporphyrinogen), has been synthesized by the reaction of diphewldiazomethane with [Ru"(L)] , which is prepared from [Ru(cod)(Cl)2] and Na4(L) 4THF. X-ray crystal studies reveal that [Ru (N)(L)] has a Cjv symmetry, and it has the usual saddle conformation, with the metal atom displaced 0.482 A out of the N4 mean plane. The reactivities and redox chemistry of this complex are summarized in Scheme 12 (see also Section 5.6.5.2). 

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