REACTIONS OF NITROSONIUM ION WITH ANIONIC CARBONYL MONOMERS AND CLUSTERS. CRYSTAL AND MOLECULAR STRUCTURE OF FeCo2(μ3-NH)(CO)9

Article abstract of DOI:10.1016/0022-328X(83)85064-5

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.