Ruthenium nitrido complexes

Table III. Binuclear Osmium and Ruthenium Nitrido Complexes...

No nitrido complexes of ruthenium(VIII) have been isolated. For osmium, the only well-established osmium(VIII) nitrido species is [0s(0)3(N)] , which has been well documented in CCC (1987). A number of heterometallic complexes formed by the interaction of [0s(0)3(N)] with a second metal center have been reported. In these complexes, the [0s(0)3(N)] ion acts as a... 

There is a rich chemistry of alkyl nitrido complexes of ruthenium(VI) and osmium(VI), which has been well documented. " ... 

Since the early 1980s rich thermal and photochemical redox chemistries of Os =N species containing nonlabile oxidation-resistant nitrogen donor ligands have emerged. However, there are only a few examples of ruthenium(VI) nitrido complexes of this type, and their redox chemistry is largely unexplored. 

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). 

Some nitrido complexes of ruthenium, osmium, and rhenium react with phosphines to give phosphineiminato complexes, as shown in Eq. (70). 

A new class of binuclear nitrido complexes of tetravalent osmium and ruthenium is described in which the metal atoms are symmetrically bridged by a nitride ligand to give a linear M-N—M unit They have the stoichiometries M2NX8(H20)2]3 and [M2N(NH3)8Y2]3+ (M = Os, Ru X = Cl, Br Y = Cl, Br, etc.). Studies are reported on their vibrational spectra, structures, and bonding. Preliminary studies are reported also on trinuclear complexes of osmium and iridium. Finally, the use of vibrational spectroscopy in the study of metal-nitrido and metal-oxo complexes is discussed briefly. 

There are now a substantial number of nitrido complexes of osmium(VI) and osmium(IV) as well as the osmiamate ion [OsVII 03N]. In addition to the ammine and ethylenediamine complexes, much recent work has been carried out on the bipy, phen and terpy complexes, often in connection with research into the photodissociation of water. The nitrosyl chemistry of the element, though seemingly not as extensive as that of ruthenium, has received much attention, and there has been considerable work on the phosphine, arsine and stibine complexes. 

Nitride, ruthenium cluster complex, 26 287 Nitrido, ruthenium clusters, 26 286 Nitrogen, iridium(III) complex, 26 119 Nitrosyls, molybdenum, 26 132 tungsten, 26 133... 

Scheme 68 Ammonia formation from a ruthenium(IV) nitrido complex upon H2 addition. ...

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