Reactions of nitrosonium ion with anionic carbonyl monomers and clusters. Crystal and molecular structure of FeCo2(μ3-NH)(CO)9 |
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Authors: | Douglas E Fjare David G Keyes Wayne L Gladfelter |
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Institution: | Department of Chemistry, University of Minnesota Minneapolis, Minnessota 55455 U.S.A. |
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Abstract: | 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 nitrogeneous ligands. When CoRu3(CO)13]? reacts with NO+, low yields of the new nitrido cluster CoRu3N(CO)12 are formed. Prior conversion of CoRu3(CO)13]? to the new hydrido cluster H2CoRu3(CO)12]? under hydrogen, followed by nitrosylation, forms the new imido cluster H2Ru3(NH)(CO)9 in very low yield. The reaction of FeCO3(CO)12]? with NO+ also generates an imido cluster, FeCo2(NH)(CO)9, in 15% 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) Å, α 95.50(1), β 100.77(1), γ 107.93(1)°. 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 CpMo(CO)3]? and CpFe(CO)2]? the N-nitrosoiminium species appears to form transient alkylmetals which further react to give the dimers CpMo(CO)3]2 and CpFe(CO)2]2. |
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