Coordination of copper within a crystalline carbon nitride and its catalytic reduction of CO.

Inherently disordered structures of carbon nitrides have hindered an atomic level tunability and understanding of their catalytic reactivity. Starting from a crystalline carbon nitride, poly(triazine imide) or PTI/LiCl, the coordination of copper cations to its intralayer -triazine groups was investigated using molten salt reactions. The reaction of PTI/LiCl within CuCl or eutectic KCl/CuCl molten salt mixtures at 280 to 450 °C could be used to yield three partially disordered and ordered structures, wherein the Cu cations are found to coordinate within the intralayer cavities.

Theoretical studies on the reaction mechanisms of the oxidation of tetramethylethylene using MOCl (M=Mn, Tc and Re).

A theoretical study on the reaction mechanisms of the addition of transition metal oxo complexes of the type MOCl (M = Mn, Tc, and Re) to tetramethylethylene (TME) is presented. Theoretical calculations using B3LYP/LACVP* and M06/LACVP* (LACVP* is a combination of the 6-31G(d) basis set along with LANL2DZ pseudopotentials on the metallic centres) were performed and the results are discussed within the framework of reaction energetics. The nature of the stability of the reaction mechanisms was equivalent for both theories.

A DFT study on the reaction mechanisms of the oxidation of ethylene mediated by technetium and manganese oxo complexes.

The oxidation of ethylene catalyzed by manganese and technetium oxo complexes of the type MOL (M = Tc, Mn, and L = O, Cl, F, OH, Br, I) on both singlet and triplet potential energy surfaces (PESs) have been studied. All molecular structures were stable on the singlet PES except for the formation of the dioxylate intermediate for the MnOL (L = O, Cl, F, OH, Br, I) catalyzed pathway. Frontier molecular orbital calculations showed that electrons flow from the HOMO of ethylene into the LUMO of the metal-oxo complex for all complexes studied except for MOL (M = Tc, Mn, and L = O) where the vice versa occurs.