Theoretical study of the mechanism for the sequential N–O and N–N bond cleavage within N₂O adducts of N-heterocyclic carbenes by a vanadium(iii) complex

Abstract

A theoretical study into the reactions of the N2O adducts of N-heterocyclic carbenes (NHCs) and a V((III)) complex was carried out using DFT calculations. Unlike most transition metal reactions with N2O that simply release N2 following O-atom transfer onto the metal centre, this NHC-based system traps the entire N2O molecule and then cleaves both the N-O and N-N bond in two consecutive reactions. The NHC presence increases the reactivity of N2O by altering the distribution of electron density away from the O-atom towards the two N-atoms. This electronic redistribution enables V-N binding interactions to form a reactive N,O-donor intermediate species. Our results show that bond breaking with concomitant ligand migration occurs via a concerted process for both the N-O and N-N cleavage reactions.

Soluble Cytotoxic Ruthenium(II) Complexes with 2-Hydrazinopyridine

“…A comparison of the calculated Ru-Cl and Ru-N bond lengths with those of reported Ru(II) complexes involving bidentate N-donor ligands reveals that the average values found for Ru-Cl (2.493 Å) is consistent with the range of the reported values {2.473 (p-cymene)Ru(curcuminato)chloro} [49]. [53].The calculation of atomic charges explains the potential donor and acceptor property of atoms [54]. The higher charge density in the 2-hydrazinopyridine ligand is allocated on nitrogen atoms of amine groups.…”

Activation of Small Molecules (H2, CO2, N2O, CH4, and C6H6) by a Porphyrinoid-Based Dimagnesium(I) Complex, an Electride

“…76,77 N 2 O is thermodynamically stable and is often used as an oxygen transfer agent in organometallic chemistry. 78−80 Here in this study, we have used N 2 O to react with 1 , which ends up in forming an oxo-bridged complex 9 . The complete reaction energy profile along with the TSs and intermediates are depicted in Figure 8.…”

“…N 2 O comprises only 6% of the total greenhouse gases and has 296 times of the global warming potential (GWP) as compared to that of CO 2 (81% of the total greenhouse gases) . N 2 O has 121 years of atmospheric lifetime, which is also much higher than that of CO 2 , viz., 30–95 years. , N 2 O is thermodynamically stable and is often used as an oxygen transfer agent in organometallic chemistry. − Here in this study, we have used N 2 O to react with 1 , which ends up in forming an oxo-bridged complex 9 . The complete reaction energy profile along with the TSs and intermediates are depicted in Figure .…”