H₂activation by hydrogenase-inspired NiFe catalyst using frustrated Lewis pair: effect of buffer and halide ion in the heterolytic H–H bond cleavage

Abstract

Hydrogen is a clean fuel alternative to fossil fuels, and it is vital to develop catalysts for its efficient activation and production.

Mechanism of Photocatalytic CO2 Reduction by Iron Spin-Crossover Complex with Copper Photosensitizer

“…We previously investigated the activation and evolution of hydrogen by complexes mimicking the hydrogenase active center (NiFe and NiIr complexes), both of which produce dihydrogen complexes as intermediates. − This is also true for the hydrogenase enzyme . Conversely, no dihydrogen complexes are formed in the present Fe complexes.…”

Metal- and ligand-substitution-induced changes in the kinetics and thermodynamics of hydrogen activation and hydricity in a dinuclear metal complex

“…For [NiFe(CO)] 2+ , which has been optimized in previous studies, the reaction barrier is very small at 0.7 kcal mol −1 . 18 Therefore, relax energy scan was performed for the distance between the oxygen of the base CH 3 COO − and the proton of the dihydrogen complex (Fig. S1 †).…”

Cyclopropanation Using Electrons Derived from Hydrogen: Reaction of Alkenes and Hydrogen without Hydrogenation

“…The INT3A reacts with the Lewis base K 2 CO 3 to give the amide type 1B (−98.5 kcal/mol). 36,37 The recovery of 2A by the reaction of 1B with H 2 is a thermodynamically favored reaction (−46.3 kcal/mol) (Figure S16). 36,37 These calculation results are consistent with the results from the radical trapping experiment (vide supra) and the stereoselectivity of the cyclopropanations (Table 1, entries 5 and 8).…”

“…36,37 The recovery of 2A by the reaction of 1B with H 2 is a thermodynamically favored reaction (−46.3 kcal/mol) (Figure S16). 36,37 These calculation results are consistent with the results from the radical trapping experiment (vide supra) and the stereoselectivity of the cyclopropanations (Table 1, entries 5 and 8). Thus, the reaction of carbenoid 3A with alkenes, unlike the concerted [2 + 1] fashion of the Simmons−Smith reaction, forms radical intermediates and gives the thermodynamically stable trans-products.…”