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The reaction of Mn-2(CO)(10) with tert-butyl isocyanide in the presence of 10 bar of carbon monoxide leads to the formation of cis- and trans-[Mn((BuNC)-Bu-t)(4)(CN)(CO)], 1a and 1b, in good yields together with [Mn((BuNC)-Bu-t)(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((BuNC)-Bu-t)(5)(CO)] units a...The reaction of Mn-2(CO)(10) with tert-butyl isocyanide in the presence of 10 bar of carbon monoxide leads to the formation of cis- and trans-[Mn((BuNC)-Bu-t)(4)(CN)(CO)], 1a and 1b, in good yields together with [Mn((BuNC)-Bu-t)(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((BuNC)-Bu-t)(5)(CO)] units as well as dinuclear anionic [Mn((BuNC)-Bu-t)(4)(CO)(mu-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-phenylcyclopent-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((BuNC)-Bu-t)(4)) (CO) (mu-CN)](2)Co(NO3)(2)}, 5, in which the cobalt atoms are tetrahedrally surrounded by the two cyanide ligands and the eta(1)-coordinated nitro groups. In contrast to the reaction of 1b, treatment of the dicyano complexes cis- or trans-[Ru((BuNC)-Bu-t)(4)(CN)(2)] with Co(NO3)(2) results in the formation of the coordination polymers {[Ru((BuNC)-Bu-t)(4)(CN)(2)]Co(NO3)(2)}(n), 7 (trans) and 9 (cis). All new compounds are characterized by X-ray diffraction experiments. (c) 2007 Elsevier B.V. All rights reserved. » weiterlesen» einklappen

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