Surface organometallic chemistry in heterogeneous catalysis

Abstract

Surface organometallic chemistry has been reviewed with a special focus on environmentally relevant transformations (C–H activation, CO2 conversion, oxidation).

Efficient “Click”‐Dendrimer‐Supported Synergistic Bimetallic Nanocatalysis for Hydrogen Evolution by Sodium Borohydride Hydrolysis

“…Since Haruta's discovery of the extraordinary efficiency of small (<5 nm) nanoparticles (NPs) in the catalysis of aerobic CO oxidation under sub‐ambient conditions in the 1980’s the use of this family of catalysts has led to considerable development at the interface between homogeneous and heterogeneous catalysis for a large number of reactions . Very small NPs bring about a good catalytic efficiency and selectivity due to the high NP surface/volume ratio and quantum confinement.…”

Polymers Based on Cyclic Carbonates as Trait d'Union Between Polymer Chemistry and Sustainable CO2 Utilization

“…Bonds introduced by nonsustainable strategies are highlighted in red. [210] The use of supported Mo, Ti,T a, or Wc atalysts in the presence of potentially renewable H 2 O 2 as oxidant (Scheme23f)i su nder investigation as ag reener method for the epoxidation of olefinicc ompounds such as fatty acids and vegetableo ils that are precursorsi nt he synthesis of bio-based carbonates. [130,137,143] Am ore sustainable approach for the esterification of bio-based polycarboxylic acids for polymer synthesis reported by MØnard et al involvede sterification of the carboxylic groups with ethanol followed by transesterification with polyalcohols catalyzed by supported CALB.…”

“…Finally,w hereas using sacrificial peroxyacids such as m-CPBA is convenienta tt he laboratory scalef or the epoxidation of olefinic groups (Scheme23e), [105,106,175] this strategy is not regarded as sustainable. [210] The use of supported Mo, Ti,T a, or Wc atalysts in the presence of potentially renewable H 2 O 2 as oxidant (Scheme23f)i su nder investigation as ag reener method for the epoxidation of olefinicc ompounds such as fatty acids and vegetableo ils that are precursorsi nt he synthesis of bio-based carbonates. [211] Improvement of the keyc atalytic step of CO 2 cycloaddition to the epoxide precursors is another viable strategy to further enhancet he sustainability of 5CCs.…”

Porous Macroligands: Materials for Heterogeneous Molecular Catalysis

“…SOMC has been established by Basset and Choplin as the reactivity of an organometallic (or coordination) compound with chemical groups at the surface of oxides, sulfides or zeolites (Figure a) . With SOMC, the elementary steps of heterogenized catalysis would obey the rules of molecular chemistry with however the restrictions that the oxide support is an additional metal‐oxo rigid ligand and that free surface species can interact with grafted catalytically active sites …”

“…[1] With SOMC, the elementary steps of heterogenized catalysis would obey the rules of molecular chemistry with however the restrictions that the oxide support is an additional metal-oxo rigid ligand and that free surface species can interact with grafted catalytically active sites. [2][3][4] To prevent eventual effect of the interactions of the active site with the oxide surface, the most drastic strategy is to get rid of the support itself. To generate self-supported molecular catalysts, the ligand of the target molecular complex is used as a building unit to construct a molecularly defined host matrix whose porosity ensure site accessibility (Figure 1b).…”