Synthesis of an Iridium Peroxido Complex and Its Reactivity Towards Brønsted Acids

Abstract

Treatment of the iridium(I) complex trans‐[Ir(4‐C5F4N)(CNtBu)(PiPr3)2] (2) with O2 or H2O2 gave the iridium(III) peroxido complex trans‐[Ir(4‐C5F4N)(O2)(CNtBu)(PiPr3)2] (3a). The peroxido complex 3a reacts with Brønsted acids to give the iridium(III) complexes cis‐[Ir(4‐C5F4N)(X)2(CNtBu)(L)(PiPr3)] (4: X = Cl, L = PiPr3, 5: X = CF3COO, L = H2O) and hydrogen peroxide. In the presence of formic acid, 3a yields the carbonato complex trans‐[Ir{κ2‐OC(O)O}(4‐C5F4N)(CNtBu)(PiPr3)2] (6) as the main product. Reactions between formic acid or dihydrogen and the iridium(I) complex 2 give the isomeric dihydrido complexes trans,trans‐[Ir(4‐C5F4N)(H)2(CNtBu)(PiPr3)2] (7a) and cis,trans‐[Ir(4‐C5F4N)(H)2(CNtBu)(PiPr3)2] (9a), respectively.

Hydrogen Addition to (pincer)IrI(CO) Complexes: The Importance of Steric and Electronic Factors

“…Measurement of the thermodynamic parameters for a cis -/ trans -dihydride isomerization is rare, albeit not unprecedented . Early work by Jesson, Muetterties, and Meakin examined the temperature dependence of the cis / trans equilibria for H 2 Fe­(PC 6 H 5 (OCH 3 ) 2 ) 4 ; the c is form was favored at high temperature .…”

The local atomic structure and thermoelectric properties of Ir-doped ZnO: hybrid DFT calculations and XAS experiments

“…11,[57][58][59] From the experimental viewpoint, the O-O bond in O 2 2À has been reported to have a length varied from 1.47 to 1.54 Å for Ir(O 2 ) complexes in organic compounds. [60][61][62] The stretching vibration of the O-O bond has been assigned 62 an IR absorption band at n = 833 cm À1 . Likewise, d O-O of 1.47 Å has been reported for a cubic zinc peroxide (ZnO 2 ).…”

Inner‐Sphere Oxygen Activation Promoting Outer‐Sphere Nucleophilic Attack on Olefins

“…It is interesting to note that the chemistry of rhodium(I) and iridium(I) complexes with oxygen is dominated by their high tendency to form peroxide complexes. [15] Notablee xceptions are af ew rhodium(I) compounds in whicho xygen remains coordinated as as imple h 2 -ligand, [16] superoxide iridium(III) derivatives, [17] or dinucleari ridium(IV) m-oxo complexes. [18] In other instances, oxygenation reactions [19] involvingC ÀOb ond formation to 1-metalla-2-oxetanes, [20] highly unstable1 -metalla-2,3dioxolanes, [21] and alkyl-hydroxy-allyl species [22] have been described,w hereash ydroxide or hydroperoxide complexes result from either oxygen insertion into MÀHb onds [23] or protonation of peroxide complexes.…”