Correlating the para-Substituent Effects on Ru(II)-Polypyridine Photophysical Properties and on the Corresponding Hybrid P450 BM3 Enzymes Photocatalytic Activity.

ABSTRACT: Ru(II)-diimine complexes covalently attached near the heme active site of P450 BM3 enzymes have been used to rapidly inject electrons and drive selective C-H functionalization upon visible light irradiation. Herein, we have generated a series of hybrid P450 BM3 enzymes containing a photosensitizer of general formula [Ru(4,4'-X₂bpy)₂(PhenA)]²⁺ where X = Cl, H, tBu, Me OPhe, OMe, or NMe₂, bpy = 2,2'-bipyridine, and PhenA = 5-acetamido-1,10-phenanthroline. We then probed the effect of electron-withdrawing and -donating groups at the para position of the 4,4'-X₂bpy ligands on the corresponding hybrid enzymes photocatalytic activity. A 3-fold improvement in initial reaction rate was noted when varying the substituent from Cl to tBu, however

SUBMITTER: Shalan H 

PROVIDER: S-EPMC5535733 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature