86743-32-0Relevant academic research and scientific papers
Synthesis, characterization and crystal structures of a series of ruthenium μ4-nitrene carbonyl clusters
Lee, Kenneth Ka Hong,Wong, Wing Tak
, p. 1707 - 1720 (2007/10/03)
Methylation of [Ru3(CO)10(NO)]- anion has led to the isolation of [Ru6(μ-H)(CO)16(μ-CO)(μ4-NH){μ 3-η2-C(O)OMe}] 1 in addition to the major product [Ru3(CO)10(NOMe)] 2. Hydrogenation of 2 in refluxing hexane gave [Ru3(μ-H)2(CO)9(NH)] 3 and [Ru3(μ-H)2(CO)9(NOMe)] 4 in moderate yields, but in the presence of [Ru3(CO)12] it gave [Ru6(μ-H)(CO)16(μ-CO)2(μ 4-NH)(μ-OMe);] 5 and [Ru5(μ-H)3(CO)13(μ 4-NH)(μ3-OMe)] 6 in addition. Thermolysis of 2 in toluene at 90°C for 3 h yielded [Ru4(CO)12(μ4-N)(μ-OMe)] 7 and [Ru6(CO)16(μ-CO)2(μ 4-NH)(μ-OMe)2] 8. Pyrolysis of 4 at 140°C for 2 h afforded [Ru6(CO)15(μ-CO)2(μ 4-NH)(μ-OMe){μ3-η2-N(H)C(O)OMe}] 9, [Ru6(μ-H)2(CO)14(μ-CO) 2{μ5-η2-NC(O)OMe}] 10 and [Ru6(CO)16(μ-CO)2(μ 4-NH)(μ-OMe)(μ-NCO)] 11 together with the known clusters [Ru4H2(CO)13] and [Ru3(μ-H)(CO)10(NH2)]. The crystal structures of 1 and 3-11 have been determined. Clusters 1, 5, 6, 8, 9 and 11 consist of a square-pyramidal 'Ru4(CO)8(μ4-NH)' moiety with four ruthenium atoms forming a square-planar base which is capped by a quadruply bridging nitrene ligand. For 1, 5, 8, 9 and 11, two additional ruthenium fragments bridge the opposite edges of the Ru4(CO)8(μ4-NH) metal core to give 'boat' form hexaruthenium nitrene compounds. Compound 6 also has a Ru4(CO)8(μ4-NH) moiety, but with only one bridging Ru(CO)4 fragment at one of the Ru-Ru edges of the tetraruthenium plane while the remaining three are bridged by hydrides. Compound 10 comprises a square-pyramidal array of five ruthenium atoms with a Ru(CO)3 unit bridging one of the Ru-Ru edges of the base. The other side of the square plane is quadruply capped by the nitrogen atom of a NC(O)OMe ligand with the oxygen atom of the acyl group bonded to the apical Ru(CO)3 unit. Compound 7 possesses a butterfly arrangement of four Ru atoms with the methoxy group bridging the hinge.
N-O bond cleavage of cluster-coordinated nitric oxide ligands using molecular hydrogen
Smieja, Joanne A.,Stevens, Robert E.,Fjare, Douglas E.,Gladfelter, Wayne L.
, p. 3206 - 3213 (2008/10/08)
The reaction of several clusters containing nitric oxide ligands with molecular hydrogen has been studied. For HRu3(CO)10(NO) the products are H2Ru3(NH)(CO)9, HRu3(NH2)(CO)10, H4Ru4(CO)12, trace amounts of H3Ru4(NH2)(CO)12, and a hexane-insoluble, THF-soluble precipitate. The compounds have been characterized by spectroscopy (including 15N NMR) and for HRu3(NH2)(CO)10 by a single-crystal X-ray crystallographic analysis (monoclinic crystal system, P21/a space group, a = 11.778 (3) ?, b = 11.928 (3) ?, c = 12.010 (4) ?, β = 98.54 (2)°, Z = 4). A system was built that allowed the reactions to be followed directly by high-pressure liquid chromatography. A kinetic analysis of the disappearance of HRu3(CO)10(NO) revealed that the reaction is first order in cluster concentration and is inhibited by CO. The rate also depends on the pressure of H2, exhibiting a saturation effect above 1400 psig. The reduction of Ru3(NOCH3)(CO)10 yields a product distribution similar to that found for HRu3(CO)10(NO) with the important exception that no hexane-insoluble species is formed. Methanol is isolated from this reaction. The major product resulting from the reduction of Ru3(NOH)(CO)10 is the same hexane-insoluble product as found for HRu3(CO)10(NO). A discussion of the mechanism of these reactions based upon the observations is presented.
REACTIONS OF NITROSONIUM ION WITH ANIONIC CARBONYL MONOMERS AND CLUSTERS. CRYSTAL AND MOLECULAR STRUCTURE OF FeCo2(μ3-NH)(CO)9
Fjare, Douglas E.,Keyes, David G.,Gladfelter, Wayne L.
, p. 383 - 394 (2007/10/02)
The reactions of several mono- and poly-nuclear carbonyl metallates with nitrosonium ion have been studied.Besides simple substitution of a carbon monoxide with NO+ some reactions yielded products containing other nitrogenous ligands.When - reacts with NO+, low yields of the new nitrido cluster CoRu3N(CO)12 are formed.Prior conversion of - to the new hydrido cluster - under hydrogen, followed by nitrosylation, forms the new imido cluster H2Ru3(NH)(CO)9 in very low yield.The reaction of - with NO+ also generates an imido cluster, FeCo2(NH)(CO)9, in 15percent yield.This cluster has been characterized by X-ray crystallography and was found to be similar to the tricobalt alkylidyne clusters. (Triclinic crystal system, P space group, Z = 2, a 6.787(1), b 8.016(1), c 13.881(2) Angstroem, α 95.50(1), β 100.77(1), γ 107.93(1) deg).Modifications of the nitrosylations using NO+ were studied.In particular, the addition of triethylamine or N-t-butylbenzaldimine allowed the use of NO+ in THF without solvent decomposition.With - and - the N-nitrosoiminium species appears to form transient alkylmetals which further react to give the dimers 2 and 2.
