Redox Non‐innocent Ligands

First-Row Transition Metal (De)Hydrogenation Catalysis Based On Functional Pincer Ligands

“…Both principles have been separately reviewed. 26,27,30,32,39,46,51,[69][70][71][72][73][74]77,78,93,[142][143][144][145] However, the direct comparison offers additional insights for catalyst design. Scheme 2.…”

Achieving Nickel Catalyzed C–S Cross-Coupling under Mild Conditions Using Metal–Ligand Cooperativity

“…In this perspective, the use of catalysts based on cheap and abundant base metals is especially beneficial for large-scale and industrial applications, where the paucity and cost of the noble metals like palladium, iridium, or ruthenium can be problematic. However, the base metals tend to react via a single electron transfer process and the corresponding two electron transfer processes are mostly enegetically uphill requiring high temperatures . In recent years, noteworthy progress has also been achieved with cheap copper , and nickel catalysts; however, these protocols almost always require high temperatures for the reaction to proceed.…”

“…The use of redox noninnocent ligands in combination with the base metals has emerged as an attractive alternative. , The ability of redox noninnocent ligands to store and release electrons when required allows multielectron transformations (mostly preferred for noble metals like palladium) with inexpensive 3d-base metals. In recent times, using the redox noninnocent properties of imine, diamine, and aminophenol based scaffolds, various new stoichiometric and catalytic reactions were developed where these organic scaffolds were found to participate actively during electron transfer processes involved during catalytic turnover .…”

Gas-Phase Synthesis and Reactivity of Ligated Group 10 Ions in the Formal +1 Oxidation State

“…A key question regarding the [(phen)M] +• metal complexes is whether they are in the +1 oxidation or +2 oxidation state (i.e. where the phen ligand is a redox non-innocent ligand [66]). An examination of the DFT calculated spin density at the metal centers in the [(phen)M] +• metal complexes reveals (Table S1) that they range from 94.7% for M = Ni to 77.8% for M = Pt.…”