Chiral N‐heterocyclic carbenes (NHCs) have become ligands of choice due to their remarkable catalytic activity in organic transformation reactions. Combining the chiral NHC ligand family and coinage metals became a productive area of research. The organometallic chemistry of coinage metals with the chiral N‐heterocyclic carbene (NHC) ligands is reviewed, with a special emphasis on the synthesis, characterization and possible applications obtained. Significant sections are devoted to the various recently developed coinage metal‐chiral NHC complexes and a detailed comparison of their activities which aims to rationalize the structure–activity relationships. Various methods of preparations of coinage metal‐chiral NHC complexes along with some typical examples of reactivity and mechanisms are covered. Cu‐chiral NHC complexes involved in conjugated additions, allylic substitutions, boration of alkenes, hydrosilylation of ketones and formation of alkenes are covered, along with some remarkable examples and reactivity of Ag‐chiral NHC complexes. Finally, applications of Au‐chiral NHC complexes in the asymmetric cyclization of ester‐functionalized 1,6‐enynes, 1,6‐enyneamines and substituted propargyloxymethanes are also reviewed.
The
development of low-cost molecular electrocatalysts for the
HER from water remains scarce. The efficient electrocatalytic hydrogen
evolution reactions (HER) with a series of sterically encumbered carbene
ligated silver(I), gold(I) and nickel(II) complexes established here
demonstrate the potential of molecular catalyst in hydrogen production
from water. Tuning the benzannulation on the coumarin-substituted
N-heterocyclic carbene (NHC) ligands afforded six new silver(I) (5–10), two new gold(I) (11 and 12), and two reported nickel(II) (13 and 14) NHC complexes, which differ by the steric bulk
around the metal atom and the counterion. Benefiting from the desirable
structure and appropriate porous morphology, complexes 6, 9, 10, and 11 exhibited
significant electrocatalytic HER activity in acidic medium with an
overpotential of −226.4, −445, −243 and −310
mV vs RHE, respectively, to drive a current density of 10 mA/cm2 when immobilized on glassy carbon electrode, which is analogous
to that of several transition metal-based nanomaterials. The kinetic
parameters such as Tafel slope value and exchange current density
for the active complexes and the former observation authenticated
the Volmer–Heyrovsky mechanism. Theoretical studies advocate
the potential of developing novel series of carbene-ligated HER electrocatalysts
based on the controlled ligand field following scalable and viable
protocols.
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