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Two <jats:italic>cis<\/jats:italic>\u2010sites, which are occupied by labile acetonitrile molecules in <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold>, are available for coordination of H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> and substituted benzoic acids. The hydroxylation of the aromatic ring occurs exclusively in the vicinity of the anchoring carboxylate functional group: <jats:italic>ortho<\/jats:italic>\u2010hydroxylation affords salicylates, whereas <jats:italic>ipso<\/jats:italic>\u2010hydroxylation with concomitant decarboxylation yields phenolates. The outcome of the substituent\u2010directed hydroxylation depends on the electronic properties and the position of substituents in the molecules of substrates: 3\u2010substituted benzoic acids are preferentially <jats:italic>ortho<\/jats:italic>\u2010hydroxylated, whereas 2\u2010 and, to a lesser extent, 4\u2010substituted substrates tend to undergo <jats:italic>ipso<\/jats:italic>\u2010hydroxylation\/decarboxylation. These two pathways are not mutually exclusive and likely proceed via a common intermediate. Electron\u2010withdrawing substituents on the aromatic ring of the carboxylic acids disfavor hydroxylation, indicating an electrophilic nature for the active oxidant. Complexes <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold> exhibit similar reactivity patterns, but <jats:bold>1<\/jats:bold> generates a more powerful oxidant than <jats:bold>2<\/jats:bold>. Spectroscopic and labeling studies exclude acylperoxoiron(III) and Fe<jats:sup>IV<\/jats:sup>\uf8feO species as potential reaction intermediates, but strongly indicate the involvement of an Fe<jats:sup>III<\/jats:sup>\uf8ffOOH intermediate that undergoes intramolecular acid\u2010promoted heterolytic O\uf8ffO bond cleavage, producing a transient iron(V) oxidant.<\/jats:p>","DOI":"10.1002\/chem.200901296","type":"journal-article","created":{"date-parts":[[2009,10,29]],"date-time":"2009-10-29T16:32:20Z","timestamp":1256833940000},"page":"13171-13180","source":"Crossref","is-referenced-by-count":98,"title":["Iron\u2010Promoted <i>ortho<\/i>\u2010 and\/or <i>ipso<\/i>\u2010Hydroxylation of Benzoic Acids with 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