[IrCl{N(CHCHPtBu₂)₂}]⁻: a versatile source of the Ir^I(PNP) pincer platform

Abstract

and N 2 , and oxidative addition of C-electrophiles, C-H bonds and dioxygen, allowing for the isolation of iridium(I) and iridium(III) (PNP) carbonyl, hydrocarbyl and peroxo complexes which were spectroscopically and crystallographically characterized.

An iridium(iii/iv/v) redox series featuring a terminal imido complex with triplet ground state

“…The Ir(PNP) fragment is trapped by solvent oxidative addition to the previously reported phenyl hydride complex [Ir(D)(C 6 D 5 )(PNP)] ( 14 ). 24 This result suggests that the lack of nitrene transfer with 9 is not attributable to steric reasons. However, the reaction with 10 might be driven by the C–H oxidative addition rather than an electrophilic nitrene transfer step, which would be expected to be more rapid for cationic 9 .…”

Homolytic N–H Activation of Ammonia: Hydrogen Transfer of Parent Iridium Ammine, Amide, Imide, and Nitride Species

“…We recently presented square-planar complexes in a wide range of formal oxidation states, such as [Ir I Cl(PNP)] − , [Ir II Cl(PNP)] ( 5 ), [Ir III Cl(PNP)] + ( 9 ), [Ir IV N(PNP)] ( 3a ), and [Ir V N(PNP)] + ( 1 ). 32 , 44 , 51 In the present study, parent iridium(II) amide and ammine complexes 6 and 7 and iridium(III) amide complex 8 were isolated and fully characterized. These compounds represent intermediates within a synthetic cycle of ammonia oxidation to dinitrogen (Scheme 17 ).…”

Square‐Planar Ruthenium(II) Complexes: Control of Spin State by Pincer Ligand Functionalization

“…The order is in line with decreasing N!Ru p-electron donation upon ligand dehydrogenation within the series 7!8!9. Accordingly, the squareplanar iridium(I) complexes [IrCO{L 1 iPr}] (n CO = 1908 cm À1 ) [26] and [IrCO{L 4 tBu}] (n CO = 1937 cm À1 ) [27] exhibit an almost identical shift, suggesting comparable electronic effects of the ligand field that are independent of the metal, oxidation state, and coordination geometries. Direct comparison of the ruthenium series 7-9 with the disilylamido pincer system is not possible, as [RuCl(CO){L Si R}] was not reported.…”