Issue 10, 2013
From the journal:

Dalton Transactions

Acidolyis and oxygen atom transfer reactivity of a diiridium hydroperoxo complex†

Thomas S. Teetsa  and  Daniel G. Nocera*a  

* Corresponding authors

a Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139-4307
E-mail: nocera@mit.edu

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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Article information

DOI
https://doi.org/10.1039/C2DT32887A
Article type
Paper
Submitted
03 Dec 2012
Accepted
03 Dec 2012
First published
10 Dec 2012

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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