Abstract
We report herein on the results of our combined experimental/computational study regarding the catalytic performance of PAd-DalPhos (L1) in nickel-catalyzed ammonia arylation for primary aniline synthesis. Primary arylamine C–N reductive eliminations occurring from arylnickel(II) parent amido complexes of the type (L)Ni(Ph)(NH2) were modeled by use of density-functional theory (DFT) methods, for a series of L1 derivatives. The dual aims were to assess the effect of structural modifications to L1 on potentially rate-limiting C–N reductive elimination and to identify promising candidates for experimental inquiry. Increasing the steric demand of the Paryl groups from o-tolyl (in L1) to mesityl (in L16) resulted in a significant lowering of the barrier to C–N reductive elimination (ΔG⧧RE), which can be attributed in part to interactions between the ligand Paryl groups and the nickel-bound amido ligand, as observed in noncovalent interaction (NCI) plots of the reductive elimination transition-state structures....
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
