A new mechanism of metal-ligand cooperative catalysis in transfer hydrogenation of ketones

Toward Efficient Direct Dynamics Studies of Chemical Reactions: A Novel Matrix Completion Algorithm

“…26,29 The reactions span gas phase, enzymatic, and catalytic chemistry and are selected based on availability of prior VTST studies, the importance of quantum and variational effects in kinetics, and the need to assess algorithm scaling and robustness. 48 This is by far the most complex reaction we could identify with the most number of internal degrees of freedom changing significantly over the course of the reaction step. 4.…”

“… Three model S N 2 Cl-substitution reactions, with methyl chloride (Cl + CH 3 Cl → ClCH 3 + Cl, six atoms, labeled ‘S N 2, C1’), α-chlorotoluene (‘S N 2, Ar1′, 16 atoms), and an α-chlorotoluene derivative consisting of five additional phenyl rings (‘S N 2, Ar6′, 66 atoms) . As the S N 2 reactions are symmetric, we only consider half of the reaction (TS to product) when constructing the X true matrix. Three hydrogen atom transfer reactions – CF 3 CH 3 + OH → CF 3 CH 2 + H 2 O, C 6 H 6 + CH 3 /C 2 H 5 → C 6 H 5 + CH 4 /C 2 H 6 , consisting of 10, 16, and 19 atoms, respectively. An example of metal–ligand cooperative homogeneous catalysis, in which the reaction step of isopropyl alcohol oxidation consists of concerted hydride transfer to the Ir metal center and proton transfer via solvent-assisted proton shuttle to the ligand (Ir catalysis, 46 atoms) . This is by far the most complex reaction we could identify with the most number of internal degrees of freedom changing significantly over the course of the reaction step. A proton transfer step in the oxidation of methylamine by methylamine dehydrogenase (MADH, 64 atoms) …”

“…An example of metal–ligand cooperative homogeneous catalysis, in which the reaction step of isopropyl alcohol oxidation consists of concerted hydride transfer to the Ir metal center and proton transfer via solvent-assisted proton shuttle to the ligand (Ir catalysis, 46 atoms) . This is by far the most complex reaction we could identify with the most number of internal degrees of freedom changing significantly over the course of the reaction step.…”

Towards Efficient Direct Dynamics Studies of Chemical Reactions: A Novel Matrix Completion Algorithm

“…An example of metal-ligand cooperative homogeneous catalysis, in which the reaction step of isopropanol oxidation consists of concerted hydride transfer to the Ir metal center and proton transfer via solvent-assisted proton shuttle to the ligand (Ir catalysis, 46 atoms). 45 This is by far the most complex reaction we could identify with the most number of internal degrees of freedom changing significantly over the course of the reaction step.…”

“…All quantum chemistry calculations are performed at the !B97X/def2-SVP level of theory 49,50 in Q-Chem (Version 5.3 or higher). 51 The sole exception is the Iridium catalyst system for which the level of theory is nearly identical to that employed in the original study, 45 with calculations carried out using the B3LYP functional 52,53 with Grimme's D3 dispersion correction using the Becke-Johnson damping (D3-BJ) function. 54,55 The Ir atom is represented using the Stuttgart small-core 'srsc' e↵ective core potential, 56,57 and all remaining atoms using the double-⇣ 6-31G* basis set.…”