Iridium nitrido complexes

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

Scheibel MG, Askevold B, Heinemaim FW, Reijerse EJ, de Bmin B, Schneider S. Closed-shell and open-shell square-planar iridium nitrido complexes. Nat Chem. 2012 4 552-558. 

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

Sieh D, Burger P. Formation of a stannyl amido complex by the reaction of a terminal iridium nitrido complex with a stannane. Z Anorg Allg Chem. 2015 641 52-55. Gloaguen Y, Rebreyend C, Lutz M, et al. An isolated nitridyl radical-bridged Rh(N-) Rh complex. Angew Chem Int Ed. 2014 53 6814-6818. 

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. 

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

Schoffel J, Rogachev AY, DeBeer George S, Burger P. Isolation and hydrogenation of a complex with a terminal iridium-nitrido bond. Angew Chem Int Ed Engl. 2009 48 4734-4738. 

Schoffel J, Susnjar N, Niickel S, Sieh D, Burger P. 4d vs. 5d—reactivity and fate of terminal nitrido complexes of rhodium and iridium. Eur J Inorg Chem. 2010 4911-4915. 

We have already alluded to the diversity of oxidation states, the dominance of oxo chemistry and the cluster carbonyls. Brief mention should be made too of the tendency of osmium (shared also by ruthenium and, to some extent, rhodium and iridium) to form polymeric species, often with oxo, nitrido or carboxylato bridges. Although it does have some activity in homogeneous catalysis (e.g. of m-hydroxylation, hydroxyamination or animation of alkenes, see p. 558, and occasionally for isomerization or hydrogenation of alkenes, see p. 571), osmium complexes are perhaps too substitution-inert for homogeneous catalysis to become a major feature of the chemistry of the element. The spectroscopic properties of some of the substituted heterocyclic nitrogen-donor complexes may yet make osmium an important element for photodissociation energy research. 

Methanol, platinum complex, 26 135 tungsten complex, 26 45 Methyl, iridium complex, 26 118 manganese complex, 26 156 osmium complex, 27 206 rhenium complexes, 26 107 Methyl acetate, iron complex, 27 184 osmium complex, 27 204 Methyl benzoate, chromium complex, 26 32 Methylene, osmium complex, 27 206 Molybdate(l -), (acetato)pentacarbonyl-, M.-nitrido-bis(triphenylphosphorus) (I-h), 27 297... 

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