Mechanistic Insights into the Ni-Catalyzed Reductive Carboxylation of C-O Bonds in Aromatic Esters with CO2 : Understanding Remarkable Ligand and Traceless-Directing-Group Effects.

The mechanism of the Ni0 -catalyzed reductive carboxylation reaction of C(sp2 )-O and C(sp3 )-O bonds in aromatic esters with CO2 to access valuable carboxylic acids was comprehensively studied by using DFT calculations. Computational results revealed that this transformation was composed of several key steps: C-O bond cleavage, reductive elimination, and/or CO2 insertion. Of these steps, C-O bond cleavage was found to be rate-determining, and it occurred through either oxidative addition to form a NiII intermediate, or a radical pathway that involved a bimetallic species to generate two NiI species through homolytic dissociation of the C-O bond. DFT calculations revealed that the oxidative addition step was preferred in the reductive carboxylation reactions of C(sp2 )-O and C(sp3 )-O bonds in substrates with extended π systems. In contrast, oxidative addition was highly disfavored when traceless directing groups were involved in the reductive coupling of substrates without extended π systems. In such cases, the presence of traceless directing groups allowed for docking of a second Ni0 catalyst, and the reactions proceed through a bimetallic radical pathway, rather than through concerted oxidative addition, to afford two NiI species both kinetically and thermodynamically. These theoretical mechanistic insights into the reductive carboxylation reactions of C-O bonds were also employed to investigate several experimentally observed phenomena, including ligand-dependent reactivity and site-selectivity.

A theoretical study on the oxidation of alkenes to aldehydes catalyzed by ruthenium porphyrins using O2 as the sole oxidant.

Density functional theory (DFT) calculations were used to study the ruthenium porphyrin-catalyzed oxidation of styrene to generate an aldehyde. The results indicate that two reactive oxidants, dioxoruthenium and monooxoruthenium-superoxo porphyrins, participate in the catalytic oxidation. In the mechanism, the resultant monooxoruthenium porphyrin acts in the tandem epoxide isomerization (E-I) to selectively yield an aldehyde and generate a dioxoruthenium porphyrin, thereby triggering new oxidation reaction cycles. In this calculation, several key elements responsible for the observed oxidative ability have been established by using Frontier molecular orbital (FMO) theory, natural bond orbital (NBO) analysis, etc., which include the reaction energy, the spin exchange effect, the spin-state conversion process, and the energy level of the lowest unoccupied molecular orbitals (LUMOs) of the reactive oxidants. The comparative oxidative abilities of the ruthenium-oxo/superoxo compounds with different axial ligands are also investigated. The results suggest that the ruthenium-oxo/superoxo species featuring a chlorine axial ligand is more reactive than that substituted with oxygen. This tuneable reactivity can be understood when considering the different electronic characters of the two ligands and the effective atomic number rule (EAN).