A catalytic synthesis of dialkylamines from alkylamines using neopentyl-substituted PNP pincer–iridium complex

Formation of a C–C double bond from two aliphatic carbons. Multiple C–H activations in an iridium pincer complex

“… 10 During the formation of 4 from 1 , three C sp 3 –H bonds are activated intramolecularly in addition to one external C sp 2 –H bond. Cyclometallation of tert -butyls 11 or other groups 12 , 13 bound to phosphorus is not unprecedented in the chemistry of iridium pincer complexes, but in the case of 4 it results in the formation of a new C–C double bond. To the best of our knowledge, this is the first example where the main product is the result of the formation of a C–C double bond from non-activated C sp 3 –H bonds.…”

Reactions of an anionic chelate phosphane/borata-alkene ligand with [Rh(nbd)Cl]2, [Rh(CO)2Cl]2 and [Ir(cod)Cl]2

“…We assume that initially a (P/borata-alkene)Ir(cod) complex 14 was generated, analogous to the formation of the Rh system 12 . However, it was apparently not persistent under the prevailing reaction conditions but underwent intramolecular C–H bond activation 20 at an ortho -methyl group of a mesityl substituent at phosphorus to give the oxidative addition product 15 ( Scheme 4 ). It was isolated in 44% yield.…”

Cobalt‐Catalyzed Dehydrogenative Coupling of Amines into Imines

“…Due to the facile reduction of imines with hydrogen gas, a more common reaction pathway under these conditions is the coupling of primary amines into secondary amines with the release of ammonia where the imine is only serving as an intermediate. This transformation has been catalyzed by a number of homogeneous ruthenium and iridium catalysts as well as heterogeneous platinum, palladium and copper catalysts.…”