Metal pi complexes of benzene derivatives Part 56. (eta(6)-fluoranthene)(tricarbonyl)chromium: isomerism and haptotropic equilibrationстатья
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Аннотация:Reaction of fluoranthene with Cr(CO)(3)Py-3/BF3 (.) OEt2 at 25 degreesC affords a mixture of two isomeric complexes: traces of tricarbonyl(1-5,15-eta(6)-fluoranthene)chromium (3) (coordination to benzene) and, as the major product, tricarbonyl(1-4,15,16-eta(6)-fluoranthene)chromium (2) (coordination to naphthalene). The ratio 3:2 is less than 0.05 according to H-1-NMR of crude product before crystallization. Complex 2 is thermodynamically less stable than 3: at 100 degreesC in decane or C6D6 for 8 h or at 90 degreesC in C6F6 for 100 h 2 rearranges irreversibly to 3 via an inter-ring haptotropic shift of the Cr(CO), group from the naphthalene moiety to the benzene part of the fluoranthene ligand. NMR evidence for a degenerate reversible haptotropic shift within the naphthalene moiety is absent. The isomers 2 and 3 have been characterized by X-ray structural analysis. (C) 2002 Elsevier Science B.V. All rights reserved.