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Issue 10, 2013
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Acidolyis and oxygen atom transfer reactivity of a diiridium hydroperoxo complex

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Abstract

Oxygenation of Ir2II,II(tfepma)2(CNtBu)2Cl3H (1, tfepma = CH3N[P(OCH2CF3)2]2) furnishes Ir2II,II(tfepma)2(CNtBu)2Cl3(OOH) (2), the first isolable iridium hydroperoxo complex. This complex transfers an oxygen atom to triphenylphosphine, producing triphenylphosphine oxide and Ir2II,II(tfepma)2(CNtBu)2Cl3(OH) (3) in high yield. Reaction of 2 with acid induces cleavage of the O–O bond, initially forming [Ir2II,II(tfepma)2(CNtBu)2Cl3(OH2)]Cl (4), which was identified by NMR spectroscopy. With HCl as the acid source, the chloride anion displaces water to form the pseudo-C2h isomer of Ir2II,II(tfepma)2(CNtBu)2Cl4 (5). With 2,6-lutidinium chloride as the acid, complex 4 forms initially and is deprotonated by the conjugate base to afford 3 as the major product.

Graphical abstract: Acidolyis and oxygen atom transfer reactivity of a diiridium hydroperoxo complex

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Publication details

The article was received on 03 Dec 2012, accepted on 03 Dec 2012 and first published on 10 Dec 2012


Article type: Paper
DOI: 10.1039/C2DT32887A
Citation: Dalton Trans., 2013,42, 3521-3527
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    Acidolyis and oxygen atom transfer reactivity of a diiridium hydroperoxo complex

    T. S. Teets and D. G. Nocera, Dalton Trans., 2013, 42, 3521
    DOI: 10.1039/C2DT32887A

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