An orthomanganation route to 2-substituted derivatives of N-methyl-1, 8-naphthalimide

N-methyl naphthalimide can be readily cyclomanganated at the 2-position, directed by the adjacent amide O atom. Di-cyclomanganation also occurs readily to attach Mn(CO)(4) groups at both 2, 7 positions. An X-ray structure determination of the mono-substituted example confirmed the five-membered metallocyclic ring. Cleavage of the Mn-C bond by HgCl2 or ICl generates 2-substituted HgCl or I derivatives respectively. Reaction of the mono-cyclomanganated N-methyl naphthalimide with phenylacetylene gives an (eta(5)-cyclohexadienyl)Mn(CO)(3) complex where the cyclohexadienyl ring has formed by two PhCCH adding in a formal [2 + 2 + 2] process across the C(1)-C(2) bond of the naphthalimide, breaking the aromaticity of the naphthalene ring as shown by a single crystal structure determination. (C) 2012 Elsevier B.V. All rights reserved.