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

The iridium(II) complex [IrCl{N(CHCHPtBu2)2}] is reduced by KC8 to give the anionic iridium(I) pincer complex [IrCl{N(CHCHPtBu2)2}]− which was isolated and fully characterized upon stabilization of the counter cation with crown ether as [K(15-cr-5)2][IrCl{N(CHCHPtBu2)2}]. This unprecedented anionic iridium(I) pincer complex completes the unusual, structurally characterized IrI/IrII/IrIII redox series [IrCl{N(CHCHPtBu2)2}]−/0/+, all in a square-planar coordination geometry, emphasizing the versatility of this PNP pincer ligand in stabilizing a broad range of oxidation states. The anionic chloro complex is a versatile source of the Ir(PNP) platform. Its reactivity was examined towards chloride ligand substitution against CO and N2, 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

CCDC 1546385: Experimental Crystal Structure Determination

GIDZAX : (t-butylcarbamato)-{2-[t-butyl(2-{[2-(di-t-butylphosphanyl)ethenyl]azanidyl}ethenyl)phosphanyl]-2-methylpropyl}-iridium(iii) benzene solvate Space Group: P 21/c (14), Cell: a 11.2846(10)Å b 14.9634(13)Å c 19.8058(17)Å, α 90° β 92.013(3)° γ 90° Related Article: Markus Kinauer, Martin Diefenbach, Heiko Bamberger, Serhiy Demeshko, Edward J. Reijerse, Christian Volkmann, Christian Würtele, Joris van Slageren, Bas de Bruin, Max C. Holthausen, Sven Schneider|2018|Chemical Science|9|4325|doi:10.1039/C8SC01113C,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

CCDC 1546382: Experimental Crystal Structure Determination

GIDYIE : (t-butylimino)-{bis[2-(di-t-butylphosphanyl)ethenyl]aminato}-iridium(iv) trifluoroacetate Space Group: P b c a (61), Cell: a 14.6519(6)Å b 15.5746(6)Å c 27.2406(10)Å, α 90° β 90° γ 90° Related Article: Markus Kinauer, Martin Diefenbach, Heiko Bamberger, Serhiy Demeshko, Edward J. Reijerse, Christian Volkmann, Christian Würtele, Joris van Slageren, Bas de Bruin, Max C. Holthausen, Sven Schneider|2018|Chemical Science|9|4325|doi:10.1039/C8SC01113C,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

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

The redox series [Ir(n)(NHx)(PNP)] (n = II-IV, x = 3-0; PNP = N(CHCHPtBu2)2) was examined with respect to electron, proton, and hydrogen atom transfer steps. The experimental and computational results suggest that the Ir(III) imido species [Ir(NH)(PNP)] is not stable but undergoes disproportionation to the respective Ir(II) amido and Ir(IV) nitrido species. N-H bond strengths are estimated upon reaction with hydrogen atom transfer reagents to rationalize this observation and are used to discuss the reactivity of these compounds toward E-H bond activation.peerReviewe