Nitrido complexes synthesis

The conversion of coordinated NSCI into a nitrido ligand provides a useful synthesis of transition-metal nitrides. For example, treatment of ReCl4(NSCl)(POCl3) with triphenylphosphine generates the nitrido complex ReNClaCPPhsla. "... 

The formation of ligands by decomposition of hydrazine or hydrazine derivatives in acidic media provides one of the standard procedures for the synthesis of rhenium nitrido complexes. ... 

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. ... 

Alternative methods for the synthesis of mononuclear Os(VI) nitrido complexes are the chemical or electrochemical oxidation of Os(II) or Os(III) ammine complexes (41-43) and the oxidation of Os(IV) complexes by organic azides (44). 

The first thionitrosyl complex was discovered by chance during an attempted synthesis of molybdenum nitrido complexes in the presence of a source of sulfur, tetrathiuram sulfide.168 This work of Dilworth and Chatt was reported in 1974 and ultimately led to the syntheses of a range of Mo, Re and Os thionitrosyl complexes starting with the respective nitrido complexes.143,164 Nitrosyl complexes, like carbonyls, had been known for decades, and the more recent syntheses of thio-carbonyl complexes forebode the advent of thionitrosyl complexes. However, convenient synthetic routes based on analogies with syntheses of NO complexes were generally not available because the requisite precursors did not exist or were inconvenient to handle. Sulfiliminato complexes (M=N=SR2) of transition metals are as yet unknown. The chemistry of thionitrosyl complexes was the subject of a recent review.179... 

Re centers are bridged by an en ligand [22]. Apparently this reaction, which involves displacement of water is not thermally rapid under the synthesis conditions. The study appears to be the first example of photosubstitution of a rhenium-nitrido complex. 

A related process has been reported for the synthesis of osmium nitrido complexes with 1,2-benzenedithiolate ligands. Thus, the synthesis of 173 was effected by treatment of (Bu4N)[OsNC14] with deprotonated 1,2-benzenedithiol (Eq. (70)). Interestingly, when 173 is treated with Me3OBF4 alkylation is observed to occur on the sulfur this contrasts the reaction of 173 with Ph3CPF6, for which reaction at the terminal nitride is observed [93]. 

Loberg MD, Fields AT (1978) Chemical structure of technetium-99m-labeled N-(2,6-dimethyl-phe-nylcarbamoylmethyl)-iminodiacetic acid ( Tc-HIDA). Int J Appl Radiat Isot 29 167-173 March A, Garuti P, Duatti A et al (1990) Synthesis of technetium(V)-nitrido complexes with chelating amines a novel class of monocationic, octahedral complexes containing the [Tc = N] core. Crystal structures of [TcN(en)2Cl] (en = ethylenediamine) and [TcN(tad)Cl] (tad = 1,5,8,12-tet-raazadodecane). Inorg Chem 29 2091-2096... 

Scheme 73 Synthesis of the terminal iridium nitrido complex [(PDI)lr=N] and acid catalyzed hydrogenation to [(PDI)lr—...

Sieh D, Schoffel J, Burger P. Synthesis of a chloro protected iridium nitrido complex. Dalton Trans. 2011 40 9512-9524. 

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