Small molecule activation with bimetallic systems: a landscape of cooperative reactivity

Abstract

There is a continous growing interest on the design of bimetallic cooperative complexes that emerges from their potential for bond activation and catalysis, a potential that has been widely exploited...

Polarized Au(i)/Rh(i) bimetallic pairs cooperatively trigger ligand non-innocence and bond activation

“…The area of bimetallic cooperativity has witnessed a rapid resurgence in the last decades, in great part due to the prospects it offers for bond activation and catalysis. 1 The same can be stated about heterogeneous 2 and enzymatic catalysis, 3 where bi- and multimetallic synergisms are at the heart of many successful chemical transformations. Beyond catalytic applications, molecular dinuclear structures offer a range of possibilities that have led to the observation of remarkable electronic, magnetic or photophysical properties, exotic bonding schemes and highly unusual reactivity, including an outstanding capacity to trap otherwise fleeting species.…”

“…Beyond catalytic applications, molecular dinuclear structures offer a range of possibilities that have led to the observation of remarkable electronic, magnetic or photophysical properties, exotic bonding schemes and highly unusual reactivity, including an outstanding capacity to trap otherwise fleeting species. 1 For instance, our group recently unlocked a new mode of ligand non-innocent behavior discernible only through a bimetallic approach. More precisely, we described the direct involvement of the widespread pentamethyl cyclopentadienyl ([C 5 Me 5 ] − , Cp*) ligand, whose popularity largely relies on its assumed robust spectator character, in the migration of a hydride from one of its methyl groups in compound [(η 5 -C 5 Me 5 )Rh(PMe 3 ) 2 ] (1a) to the rhodium centre ( Fig.…”

Widening the Landscape of Small Molecule Activation with Gold‐Aluminyl Complexes: A Systematic Study of E−H (E=O, N) Bonds, SO2 and N2O Activation

“…The eye‐catching analogies illustrated here between E−E and Au/Cu−Al bonds, in terms of both bonding features and related reactivity, suggest that gold‐aluminyl complexes may be versatile systems for activating either stoichiometrically or catalytically a wide range of small molecules. Note that, on a more general context, the interest around small molecule activation processes mediated by bimetallic systems in a cooperative way is currently of extreme interest due to the high tunability of the metal‐metal bonding features [22,23] …”

“…Note that, on a more general context, the interest around small molecule activation processes mediated by bimetallic systems in a cooperative way is currently of extreme interest due to the high tunability of the metal-metal bonding features. [22,23] One attractive perspective concerns the activation of EÀ H (E = O, N) bonds in water and ammonia, respectively. An efficient activation of OÀ H bonds in water, for instance, is a crucial initial step for the production of dihydrogen from water splitting.…”

On the Dynamic Behavior of Pacman Phosphanes─A Case of Cooperativity and Redox Isomerism

“…In the last few years, bimetallic complexes opened a field for new, more selective or efficient pathways in activation chemistry, often inspired by nature. − Recently, growing interest in cooperative behavior of main group elements including even non-metals evolved. − A basic requirement for cooperative reactivity is close proximity of the interacting centers. Among several other systems, this can be achieved by the usage of Pacman ligands. − …”