Vibrational Control of Covalency Effects Related to the Active Sites of Molybdenum Enzymes.

ABSTRACT: A multitechnique spectroscopic and theoretical study of the Cp₂M(benzenedithiolato) (M = Ti, V, Mo; Cp = η⁵-C₅H₅) series provides deep insight into dithiolene electronic structure contributions to electron transfer reactivity and reduction potential modulation in pyranopterin molybdenum enzymes. This work explains the magnitude of the dithiolene folding distortion and the concomitant changes in metal-ligand covalency that are sensitive to electronic structure changes as a function of d-electron occupancy in the redox orbital. It is shown that the large fold angle differences correlate with covalency, and the fold angle distortion is due to a pseudo-Jahn-Teller (PJT) effect. The PJT effect in these and related transition metal dithiolene systems a

SUBMITTER: Stein BW 

PROVIDER: S-EPMC7908822 | biostudies-literature | 2018 Nov

REPOSITORIES: biostudies-literature