136576-14-2Relevant articles and documents
Synthesis and reduction of osmium(VI) nitrido complexes and X-ray crystal structure of tetra-n-butylammonium octachlorodinitrido(μ-pyrazine)diosmate(VI)
Ware, David C.,Taube, Henry
, p. 4598 - 4605 (2008/10/08)
Anionic and neutral osmium(VI) nitrido complexes are prepared by the substitution of mono- or polypyridyl ligands on [n-Bu4N][OsNCl4] (1) in nonaqueous solvents. The cationic complex [OsNCl2(terpy)]+ (11) is formed by chelate ring closure of OsNCl3(η2-terpy) (9) in H2O. The complexes were characterized by UV-vis, 1H NMR, and IR spectroscopy. 15N-labeled complexes were prepared to assign v(Os≡N) unambiguously. Reduction of the nitrido complexes in protic media produced the monoammine complexes with intact coordination spheres. The structure of the pyrazine-bridged nitrido binuclear species (3) was determined by a single-crystal X-ray structure analysis. It crystallizes in the space group P1 with a = 11.557 (4) A?, b = 11.582 (3) A?, c = 11.028 (2) A?, α = 113.02 (2)°, α = 108.67 (2)°, γ = 91.81 (2)°, V = 1266 A?3, and Z = 1. The structure was refined to R = 0.049 and Rw = 0.066 for 3906 reflections with Fo2 > 3σ (Fo2). The pyrazine nitrogen atoms coordinate to two OsNCl4 fragments in the position trans to the nitride, resulting in a tetragonally distorted octahedral geometry about each osmium center. The Os≡N bond length is 1.630 (7) A? with the osmium atoms displaced 0.365 A? from the plane containing the four chloride ligands.
