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This book represents the detailed work of A. Chatterjee. Inspired by Whitesides, the biotin-(strept)avidin technology has been exploited to localize a biotinylated metal cofactor within (strept)avidin in Ward group. Optimization of the performance of the resulting artificial metalloenzymes is best achieved relying on chemogenetic means: combining a collection of biotinylated organometallic cofactors with a library of streptavidin mutants. Relying on this strategy, artificial metalloenzyme based on the biotin-streptavidin technology have been developed for three C-C bond forming reactions: Suzuki cross-coupling, C-H bond activation, and olefin metathesis. A variety of biotinylated N-heterocycliccarbene- (NHC) and bulky phosphine ligands were synthesized and tested with palladium, rhodium and ruthenium catalysts for this purpose.