Tricarbonylchromium complexes of aryl triflates undergo base-mediated anionic thia-Fries rearrangements to generate push-pull substituted [ortho-hydroxyaryl(trifluoromethylsulfonyl)phenol]tricarbonylchromium complexes under very mild reaction conditions.

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Organo-chromium compounds S 5500Unanticipated Formation of ortho-Sulfone Substituted Phenols by Anionic Thia-Fries Rearrangement of (Aryl triflate)tricarbonylchromium Complexes. -Tricarbonylchromium complexes of aryl triflates (V), (VII), (IX) and (XI) undergo base-mediated anionic thia-Fries rearrangement to generate push-pull substituted ortho-(trifluoromethylsulfonyl)phenol complexes (VI), (VIII), (X) and (XII) under very mild conditions. This pathway is in contrast to the chemistry of the uncomplexed ligand systems, which usually react with benzyne formation. -(ZHAO, Z.; MESSINGER, J.; SCHOEN, U.; WARTCHOW, R.; BUTENSCHOEN*, H.; Chem. Commun. (Cambridge) 2006, 28, 3007-3009; Inst. Org. Chem., Univ. Hannover, D-30167 Hannover, Germany; Eng.) -M. Paetzel 48-184

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The new cluster [Co6(μ3-S)2(CO)14(μ4-η2-SPC6H4OMe)] 1 was isolated from the reaction of Co2(CO)8 with dimers of p-methoxyphenylthionophosphine sulfide, and its structure 1 has been determined by single crystal X-ray diffraction.