Homolytic N-H Activation of Ammonia: Hydrogen Transfer of Parent Iridium Ammine, Amide, Imide, and Nitride Species.
Scheibel, Markus G. ; Abbenseth, Josh ; Kinauer, Markus ; Heinemann, Frank W. ; Würtele, Christian ; de Bruin, Bas ; Schneider, Sven
Citable Link (URL):http://resolver.sub.uni-goettingen.de/purl?gs-1/12282
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.
Sponsored by EU
Project: Catalytic Carbene Insertion Reactions; Creating Diversity in (Material) Synthesis (CATCIR)