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Metal–ligand cooperativity (MLC) is an established strategy for developing effective hydrogenation and dehydrogenation catalysts. Metal–metal cooperativity (MMC) in bimetallic complexes is not as well understood, and to date has had limited implementation in (de)hydrogenation. Herein we use (de)hydrogenation processes as a platform to examine modes of cooperativity, with a particular focus on catalytic mechanisms. We investigate how lessons learnt from the extensive development of metal–ligand cooperative catalysts can aid the ongoing development of metal–metal cooperative catalysts. [ABSTRACT FROM AUTHOR]

This review summarises the most recent advances in Ir–NHC catalysis while revisiting all the classical reactions in which this type of catalyst has proved to be active. The influence of the ligand system and, in particular, the impact of the NHC ligand on the activity and selectivity of the reaction have been analysed, accompanied by an examination of the great variety of catalytic cycles hitherto reported. The reaction mechanisms so far proposed are described and commented on for each individual process. Moreover, some general considerations that attempt to explain the influence of the NHC from a mechanistic viewpoint are presented at the end of the review. The first sections are dedicated to the most widely explored reactions that use Ir–NHCs, i.e., hydrogenation and transfer hydrogenation, for which a general overview that tries to compile all the Ir–NHC catalysts hitherto reported for these processes is provided. The next sections deal with hydrogen borrowing, hydrosilylation, water splitting, dehydrogenation (of alcohols, alkanes, aminoboranes and formic acid), hydrogen isotope exchange (HIE), signal amplification by reversible exchange and C–H bond functionalisation (silylation and borylation). The last section compiles a series of reactions somewhat less explored for Ir–NHC catalysts that include the hydroalkynylation of imines, hydroamination, diboration of olefins, hydrolysis and methanolysis of silanes, arylation of aldehydes with boronic acids, addition of aroyl chlorides to alkynes, visible light driven reactions, isomerisation of alkenes, asymmetric intramolecular allylic amination and reactions that employ heterometallic catalysts containing at least one Ir–NHC unit. [ABSTRACT FROM AUTHOR]

Oxidation and hydrogenation catalysis plays a crucial role in the current chemical industry for the production of key chemicals and intermediates. Because of their easy separation and recyclability, supported catalysts are widely used in these two processes. Layered double hydroxides (LDHs) with the advantages of unique structure, composition diversity, high stability, ease of preparation and low cost have shown great potential in the design and synthesis of novel supported catalysts. This review summarizes the recent progress in supported catalysts by using LDHs as supports/precursors for catalytic oxidation and hydrogenation. Particularly, partial hydrogenation of acetylene, hydrogenation of dimethyl terephthalate, methanation, epoxidation of olefins, elimination of NOx and SOx emissions, and selective oxidation of biomass have been chosen as representative reactions in the petrochemical, fine chemicals, environmental protection and clean energy fields to highlight the potential application and the general functionality of LDH-based catalysts in catalytic oxidation and hydrogenation. Finally, we concisely discuss some of the scientific challenges and opportunities of supported catalysts based on LDH materials. [ABSTRACT FROM AUTHOR]