Catalytic Activity of Molybdenum Complexes Bearing PNP‐Type Pincer Ligand toward Ammonia Formation

Abstract

We newly designed and prepared a novel molybdenum complex bearing a 4‐[3,5‐bis(trifluoromethyl)phenyl]pyridine‐based PNP‐type pincer ligand, based on the bond dissociation free energies (BDFEs) of the N−H bonds in molybdenum‐imide complexes bearing various substituted pyridine‐based PNP‐type pincer ligands. The complex worked as an excellent catalyst toward ammonia formation from the reaction of an atmospheric pressure of dinitrogen with samarium diiodide as a reductant and water as a proton source under ambient reaction conditions, where up to 3580 equivalents of ammonia were formed based on the molybdenum atom of the catalyst. The catalytic activity was significantly improved by one order of magnitude larger than that observed when using the complex before modification.

Computational design of cooperatively acting molecular catalyst systems: carbene based tungsten- or molybdenum-catalysts with rhodium- or iridium-complexes for the ionic hydrogenation of N2 to NH3

“…61 Structures like 2 di (one bridging N 2 moiety) are well known for example from the many Mo-NN-Mo complexes introduced by the Nishibayashi group. 29,30 Assessing the feasibility of dimerization, we studied both tungsten and molybdenum pincer complexes, featuring ligands L1, L10, and L11. Gratifyingly, the formation of 1 di proved to be highly unlikely for all tungsten/molybdenum pincer complexes, with energy ranging from 44.5 to 56.7 kcal mol −1 (Fig.…”

“…[22][23][24][25] The most recent and impressive developments in catalytic ammonia formation using N 2 /H + /e − were achieved mainly by the groups of Nishibayashi, Nishibayashi/Yoshizawa and Peters. [26][27][28][29][30] With regard to the N 2 /H 2 reaction system, Schneider, Holthausen, and co-workers 31 have observed that the nitrogen center of molecular ruthenium pincer nitrides, which are potentially engaged in an N 2 /H 2 catalytic cycle, can undergo conversion into NH 3 upon exposure to H 2 . Notably, Hou et al 32 revealed the potential of trinuclear titanium hydrides in breaking the NuN triple bond in the presence of H 2 .…”

“…22–25 The most recent and impressive developments in catalytic ammonia formation using N 2 /H + /e − were achieved mainly by the groups of Nishibayashi, Nishibayashi/Yoshizawa and Peters. 26–30…”

Microwave-Assisted Synthesis of Flower-like MnMoO4 Nanostructures and Their Photocatalytic Performance

“…They have been extensively used as environmental remediation materials because of their exceptional performance in photocatalysis. Molybdenum oxides have garnered significant attention in recent times for their potential applications in several domains, such as humidity sensors, magnetic fields, the microwave approach, optical fibers, scintillator materials, photoluminescence devices, catalysis, and electrochemical sensors, owing to their physiochemical characteristics [18][19][20][21]. Adding certain precious metals to the oxides can enhance their optical, catalytic, and sensing properties.…”