Panida SurawatanawongOleg V. OzerovTexas A and M UniversityMahidol University2018-05-032018-05-032011-05-17Organometallics. Vol.30, No.11 (2011), 2972-297915206041027673332-s2.0-79958135935https://repository.li.mahidol.ac.th/handle/20.500.14594/11715This work presents the investigation by DFT methods of the mechanism of N-Me and N-H oxidative addition in reactions of the secondary amine form of the PNP pincer ligand 4-Me-2-( i Pr 2 P)-C 6 H 3 ) 2 NH (or PN(H)P), its N-methylated derivative 4-Me-2-( i Pr 2 P)-C 6 H 3 ) 2 NMe (or PN- (Me)P), and a version of the latter whose aromatic rings are "tied" with a CH 2 CH 2 linker (or T PN(Me)P) with Rh(I) and Ir(I). Reactions were considered by starting from (Κ 3 -PN- (H)P)MCl, (Κ 3 -PN(Me)P)MCl, and (Κ 3-T PN(Me)P)MCl(M = Rh, Ir). Oxidative addition from (Κ 3 -PN(H)P)MCl to give (PNP)M(H)(Cl) is predicted to proceed with essentially no barrier via direct migration ofHfromNto the metal. The analogous direct migration of Me fromNto the metal is predicted to be the dominant mechanism for both Rh systems, with the calculated barrier for (Κ 3 -PN(Me)P)RhCl of 21.8 kcal/mol being in reasonable agreement with the experimental value of 24.0(18) kcal/mol. For Ir, an alternative pathway that involves initial NCH 2 -H oxidative addition, followed by CH 2 extrusion and C-Hrecombination, is calculated to be competitive with direct Me transfer, especially for the "tied" ligand where it is preferred. This alternative pathway entails prohibitively high barriers for both Rh systems ( > 35 kcal/mol), which can be traced to the high energy of the intermediate in which a CH 2 carbene is bound to a Rh III center. In general, the energies of all barriers and intermediates are lower with the "tied" ligand. DFT calculations also evaluate the energetics of the NCH 2 -H oxidative addition intermediates. These were observed experimentally for only the "tied" ligand system (for both Rh and Ir), and the DFT energies are consistent with these observations. © 2011 American Chemical Society.Mahidol UniversityChemistryArticleSCOPUS10.1021/om200020b