Natural inspirations for metal–ligand cooperative catalysis

A catalytically active [Mn]-hydrogenase incorporating a non-native metal cofactor

“…We previously reported that deprotonation of the 2 -OH group was a key step in enabling H 2 activation by a semi-synthetic [Fe]-hydrogenase 12. After deprotonation, the anionic 2 -O − group served as an internal base to assist in the heterolytic splitting of H 2 at the Fe center 12,13. The need for a base for H 2 splitting by 3 suggested that a similar mechanism was operating in the activation of H 2 by 3 .…”

Triple the fun: tris(ferrocenyl)arene-based gold(i) complexes for redox-switchable catalysis

“…Attaining control over catalytic reactions by external stimuli, preferably with as tight a grip as demonstrated in Nature's complex regulation pathways, has long been at the centre of interest for the chemical community. [1][2][3] It has been 25 years since the seminal work by the groups of Wrighton and Rebek, the former demonstrating a cobaltocene-based rhodium complex A (Chart 1) to function as either a good hydrogenation (Co II ) or hydrosilylation (Co III ) catalyst, the activity for the corresponding reaction being signicantly lower in the respective other oxidation state. 4 Rebek and co-workers used light to reversibly isomerise an azobenzene-derived organo-catalyst B and thus tuning it towards an amide-forming reaction.…”

Recent advances in the mechanisms of the hydrogen evolution reaction by non-innocent sulfur-coordinating metal complexes

“…Several hydrogenases mimicking metal complexes based on Earth-abundant metals have been reported since the unraveling of the structure of hydrogenases from bacteria such as Desulfovibrio gigas and Clostridium pasteurianum. [111][112][113][114][115][116][117] Two thiolates of cysteine residues and an additional CO ligand bridge the two metals. Furthermore, one Fe center is coordinated by a thiolate of the cysteine residue in a terminal fashion.…”