The reaction of manganese carbonyl with tert-butylisocyanide: Synthesis and characterization of cis- and trans-[Mn(BuNC)4(CN)(CO)] |
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| Authors: | Kathi Halbauer |
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| Affiliation: | Friedrich-Schiller-University, Institute of Inorganic and Analytical Chemistry, Lessingstr. 8, 07743 Jena, Germany |
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| Abstract: | The reaction of Mn2(CO)10 with tert-butyl isocyanide in the presence of 10 bar of carbon monoxide leads to the formation of cis- and trans-[Mn(tBuNC)4(CN)(CO)], 1a and 1b, in good yields together with [Mn(tBuNC)6]CN (2), as a minor product. Nevertheless, the reaction pathway highly depends on the reaction conditions. An interesting side-product is obtained, if chloroform is used during the workup procedure. Compound 3 is composed of cationic [Mn(tBuNC)5(CO)] units as well as dinuclear anionic [Mn(tBuNC)4(CO)(μ-CN)MnCl3] moieties. If no additional CO pressure is applied to the system, the organic product N,N′-di-tert-butyl-3,5-bis-tert-butylimino-4-phenyl-cyclopent-1-ene-1,2-diamine (4), is formed in considerable amount. Compound 4 most probably is produced via a double benzylic C-H activation of the solvent toluene and the oligomerization of four isocyanide moieties. The reaction of 1b with Co(NO3)2 leads to the isolation of the trinuclear cyanide bridged coordination compound {[Mn(tBuNC)4) (CO) (μ-CN)]2Co(NO3)2}, 5, in which the cobalt atoms are tetrahedrally surrounded by the two cyanide ligands and the η1-coordinated nitro groups. In contrast to the reaction of 1b, treatment of the dicyano complexes cis- or trans-[Ru(tBuNC)4(CN)2] with Co(NO3)2 results in the formation of the coordination polymers {[Ru(tBuNC)4(CN)2]Co(NO3)2}n, 7 (trans) and 9 (cis). All new compounds are characterized by X-ray diffraction experiments. |
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| Keywords: | Manganese Isocyanide ligands Cyanide ligands Coordination polymers X-ray |
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