Theoretical mechanism studies on the competitive CO-induced N–N bond cleavage of N2O with N–O bond cleavage mediated by (η5-C5Me5)Mo[N(iPr)C(Me)N(iPr)](CO)2

Abstract

The reaction mechanism for CO-induced reduction of N2O mediated by (η(5)-C5Me5)Mo[N((i)Pr)C(Me)N((i)Pr)](CO)2 is studied using density functional theory (DFT). Two competitive pathways for the N-O and N-N bond cleavage are investigated in detail. The former generates N2, CO and a coproduct terminal Mo oxo complex, which is attacked by two CO to recycle the catalyst via oxygen atom transfer (OAT) in a four-step process. The latter contains three steps yielding a nitrosyl, isocyanate complex. The N-N bond cleavage occurs in step 3. The barriers of the key steps are numerically similar in the two paths. The calculated proportion of products is consistent with the experiment. The competition of N-O and N-N bond cleavage is also supported by NBO analysis.

A theoretical investigation on palladium-catalyzed one-pot coupling of aryl iodides, alkynes, and amines through CN bond cleavage for the synthesis of indole derivatives

“…The amination of path B is also via TS8 . It is known that the larger the overlap of (+), (−) phase wave function between bonding atoms, the more readily the bond forms . Yet both the (−) phase of N2 and the (+) phase of C4 are too small to facilitate the formation of C4N2 bond.…”

“…It is known that the larger the overlap of (1), (2) phase wave function between bonding atoms, the more readily the bond forms. [41] Yet both the (2) phase of N2 and the (1) phase of C4 are too small to facilitate the formation of C4AN2 bond. Besides, the contribution from orbitals of bonding atoms to HOMO were calculated ( Table 3).…”

Theoretical Investigation on the Mechanism and Selectivity of Catalyst-Free Annulation of Ynediones and (Iso)quinoline N-Oxides

“…Quantitatively, the yield 3aa/4aa could be predicted by employing exothermic or barrier differences between competitive paths. [26][27][28][29][30] The ratio is calculated to be far greater than 99/1 using a difference of 4.26 or 8.88 kcal mol −1 . This just reflects the existence rationality of another bNhn and aNhn paths.…”

Theoretical investigation on the mechanism and enantioselectivity of organocatalytic asymmetric Povarov reactions of anilines and aldehydes

“…In view of the great impact of solvent effect on reaction involving ions, it is logical that no large discrepancy existing for this neutral system on the overall trend of relative energy profiles in solution and gas phase. So the solvation influence can be estimated by our approach [41][42][43]. The free energies of all optimized structures in solution phase are lower than those in gas phase (Table S1).…”

“…Besides, the contribution from orbitals of bonding atoms was calculated using Multiwfn_3.7_dev (Table 2) [38,42]. It is known that the delocalization of electron density is beneficial for the stability of intermediate structure [41][42][43][44]. As can be seen from HOMO of int5, the electron density is mainly distributed on phenyl ring and electronegative N2, which denotes the π electron transfer from enamine to arylimine in two times of nucleophilic attacks realizing [2 + 2] cycloaddition.…”