Mechanistic Views on First-row Earth-Abundant Transition Metal Catalyzed Ullmann-type O-Arylation Reactions

Transition metal-catalyzed reactions  have attracted much attention in synthetic organic chemistry due to their important role in the formation of C-heteroatom bonds. Ullmann coupling has risen in prominence in recent decades owing to its utilization in the synthesis of biaryl ethers found in a wide range of natural products together with biologically essential molecules, including antibiotics and major industrial polymers. In this article we provide the current understanding of the theoretical aspects of the underlying mechanism of the Ullmann-type O-arylation reaction.

Comprehensive computational study on reaction mechanism of N-Nitroso dimethyl amine formation from substituted hydrazine derivatives during ozonation

N- Nitrosodimethyl amine, the simplest member of the N-Nitrosamine family, is a carcinogenic and mutagenic agent that has gained considerable research interest owing to its toxic nature. Ozonation of industrially important hydrazines, such as unsymmetrical dimethylhydrazine (UDMH) or monomethylhydrazine (MMH), has been associated with NDMA formation and accumulation in the environment. UDMH/MMH - ozonation also leads to several other transformation products such as acetaldehyde dimethyl hydrazine (ADMH), tetramethyl tetra azene (TMT), diazomethane, methyl diazene, etc, which can be either precursors or competitors for NDMA formation. However, the relevant chemistry detailing the formation of these transformation products from UDMH/MMH -ozone reaction and their subsequent conversion to NDMA is not well understood. In this work, we explored the formation mechanism of ADMH and TMT from UDMH-ozonation and their further oxidation to NDMA using the second-order Moller Plesset perturbation theory employing the 6-311G(d) basis set. We have also investigated how MMH selectively forms methyl diazene and diazomethane under normal conditions and NDMA in the presence of excess ozone. Our calculations indicate that the reactions proceed via an initial H abstraction from the hydrazine –NH2 group, followed by the oxidation of the generated N-radical species. The formation of ADMH from the UDMH-ozone reaction involves an acetaldehyde intermediate, which then reacts with a second UDMH molecule to generate ADMH. The preferable attack of ozone molecule on N=C bond of ADMH generates DMAN intermediate, which subsequently undergoes oxidation to form NDMA. Unlike other transformation products, TMT formation occurs via the dimerization of DMAN. 1Though there exists an N=N bond in the TMT, which are preferable attacking sites for ozone, experimental studies show the lower yields of NDMA formation, which corroborates with the high activation barrier required for the process (42 kcal/mol). Overall, our calculated results agree well with the experimental observations and rate constants. Computational calculations bring new insights into the electronic nature and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally

A Quantum Chemical Investigation into the Molecular Mechanism of the Atmospheric Reactions of Chemi-Ions with Nitrogen and Nitrogen Oxides

Nitrogen oxides and chemi-ions are atmospheric pollutants with considerable aeronomic interest. These toxicants can react with each other, producing various ionic species and highly reactive by-products that play a crucial role in aerosol clustering and mediate several important atmospheric reactions. Understanding the chemical reactivity of these pollutants can provide essential information for controlling their excess emission into the atmosphere. Computational modeling and electronic structure studies help in predicting the structure, reactivity, and thermodynamics of transient atmospheric chemical species and can guide experimental research by providing vital mechanistic insights and data. In the present study, a computational investigation into the mechanisms of the binary associative reactions between negative ions: O2− and O3− with NO, NO2, and N2 was conducted using the Coupled-Cluster Singles and Doubles (CCSD) theory. Five model reactions between N2/NOx with On− (n = 2, 3) were considered in this work. Our calculations revealed that reactions (2) and (5) are two sequential processes involving intermediates, and all others occur in a concerted manner by direct transitions from the reactants to the products, with no isolable intermediates proceeding via single non-planar transition states. Our study revealed that the higher activation barrier required for the formation of NO3− (2) as compared to NO2− (1) could be the reason for the excess formation of NO2− ions over NO3− ions in the atmosphere. Further, all the investigated reactions except (5) are found to be feasible at room temperature. The energy required to break N-N bonds in the N2 molecule justifies the high barrier for (5). The results obtained from the study are in close agreement with the available experimental data. Moreover, the data from the study can be utilized for the evaluation of experiments and model predictions pertaining to NOx oxidation and molecular modeling of the gas-phase chemistry of pollutants/nucleation precursors formed in the Earth’s atmosphere and aircraft engines