Acidolyis and oxygen atom transfer reactivity of a diiridium hydroperoxo complex

作者：Teets Thomas S; Nocera Daniel G^*

来源：Dalton Transactions, 2013, 42(10): 3521-3527.

DOI：10.1039/c2dt32887a

Oxygenation of Ir-2(II, II)(tfepma)(2)((CNBu)-Bu-t)(2)Cl3H (1, tfepma = CH3N[ P(OCH2CF3)(2)](2)) furnishes Ir2(II,II)(tfepma)(2)((CNBu)-Bu-t)(2)Cl-3(OOH) (2), the first isolable iridium hydroperoxo complex. This complex transfers an oxygen atom to triphenylphosphine, producing triphenylphosphine oxide and Ir2(II, II)(tfepma)(2)(CNtBu)(2-)Cl-3(OH) (3) in high yield. Reaction of 2 with acid induces cleavage of the O-O bond, initially forming Ir2(II,II()tfepma)(2)(CNtBu) Cl-2(3)(OH2)] Cl (4), which was identified by NMR spectroscopy. With HCl as the acid source, the chloride anion displaces water to form the pseudo-C(2)h isomer of Ir2(II,II)(tfepma)(2)((CNBu)-Bu-t)(2)Cl-4 (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.

• 出版日期2013