Binuclear Cooperative Catalysts for the Hydrogenation and Hydroformylation of Olefins

Abstract

Cooperative activation of substrates simultaneously by a (transition) metal and a protein residue is a common strategy in enzyme catalysis. Cooperative dinuclear catalysis for synthetic systems is relatively underdeveloped. Here, we focus on some examples of dinuclear hydrogenation and hydroformylation reactions, with the aim to stimulate the scientific community to develop more catalytic processes based on cooperative dinuclear systems.

A Switchable Gold Catalyst by Encapsulation in a Self‐Assembled Cage

“…Moreover, reaction rates and product distribution can be greatly affected by catalyst encapsulation. Interestingly, many catalytic reactions operate through a dinuclear mechanism or deactivate via a dinuclear pathway; by encapsulation of a transition metal complex, such decomposition pathways can be suppressed, leading to higher catalytic turnover numbers …”

“…[4] Moreover,r eaction rates [5] and productd istribution [6] can be greatlya ffected by catalyst encapsulation. Interestingly, many catalytic reactions operate through ad inuclear mechanism [7] or deactivate via ad inuclearp athway; [8,9] by encapsulation of at ransition metal complex, such decomposition pathways can be suppressed, leading to higher catalytic turnover numbers. [10] In principle, an encapsulatione ventc ould also change the catalyticp athway of ar eaction, and as such can be used as as witch for ac atalytict ransformation.…”

“…Gold catalyzed conversion of 4-phenyl-1-butyne. [a] = 33 mm,[ 7] = 33 mm.Y ields are averaged from two measurements.…”

Titanate Nanotube-Supported Au–Rh Bimetallic Catalysts: Characterization and Their Catalytic Performances in Hydroformylation of Vinyl Acetate

“…It is well known that the catalytic activity and selectivity of poly metallic catalyst are usually quite different from those of monometallic catalyst due to the synergistic effects [28][29][30][31]. However, there are also positive changes as the polymetallic catalyst consists of intermediates, which have both multi-metallic and monometallic compounds [32][33][34][35]. Klahn et al reported that the synergism of rhodium and rhenium in the complexes could dramatically enhance the catalytic performance in catalytic hydroformylation [36].…”

Facile high-yield synthesis of unsymmetric end-off compartmental double Schiff-base ligands: easy access to mononuclear precursor and unsymmetric dinuclear complexes

“…Moreover, bimetallic complexes also play an important role in catalytic processes and novel abiotic molecule transformations. The concept of cooperative reactivity based on bimetallic catalysts [13][14][15] has lead to interesting applications such as asymmetric rearrangements, 16 ring opening reactions, 17 hydroalkoxylation of alkynes, 18 palladium-assisted C-X bond formation 19 and polymerizations. 20,21 Over the past decades compartmental ligands capable of coordinating multiple metal ions have been an intense area of research.…”