Computational study of the highly efficient conversion of methane to methanol with mercury (II) catalysts

Reductive functionalization of 3d metal–methyl complexes: The greater importance of ligand than metal

“…6 In 1995, Periana and coworkers studied the catalytic conversion of methane to methanol by HgF + ion using ab initio methods. 7 In another study, platinum catalysts were studied experimentally for direct oxidation of methane to a methanol derivative at low temperature. 8 In recent research by Periana et al oxidative functionalization of ethane was studied with a Pt(II) catalyst resulting in fast and selective reactions.…”

C−H Activation at a Cationic Platinum (II) Center: A Quantum Chemical Investigation

“…The latter mechanism has been suggested for the Shilov reaction. , However, in that reaction water is the solvent, and the polarity and proton affinity thereof are described as crucial. Quantum chemical studies of methane activation at electrophilic late transition metal centers include those of Siegbahn and Crabtree, Horsley et al, Mylvaganam et al, Su and Chu, and Hill and Puddephatt . All of these studies include interactions with solvents with some capability of solvating protons.…”

Theoretical Study of Two Possible Side Reactions for Reductive Functionalization of 3d Metal–Methyl Complexes by Hydroxide Ion: Deprotonation and Metal–Methyl Bond Dissociation

“…11−14 For example, in research by Periana and co-workers, the conversion of methane to methanol with a Hg II catalyst model (HgF + ) was studied by ab initio computational methods. 11 The efficiency of the reaction was high, and it was found to be improved by the high solvation energy of the proton. 11 In another computational study by Periana and co-workers, a catalytic mechanism was modeled for the functionalization of a metal−carbon bond.…”

“…11 The efficiency of the reaction was high, and it was found to be improved by the high solvation energy of the proton. 11 In another computational study by Periana and co-workers, a catalytic mechanism was modeled for the functionalization of a metal−carbon bond. 12 The mechanism deduced from theory was similar to that previously reported by the same research group in which C−H activation occurs via an alkoxo complex (M−OR, M = Ir III ), producing M−R and the desired functionalized product, R− OH.…”

“…Oxidation of light alkanes to their corresponding alcohols, especially methane to methanol, has attracted much attention recently. − Various computational studies have been done of the catalytic conversion of light alkanes to alcohols. − For example, in research by Periana and co-workers, the conversion of methane to methanol with a Hg II catalyst model (HgF + ) was studied by ab initio computational methods . The efficiency of the reaction was high, and it was found to be improved by the high solvation energy of the proton .…”