Noninnocent Dithiolene Ligands: a New Oxomolybdenum Complex Possessing a Donor-acceptor Dithiolene Ligand

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2010 May 21

PMID 20481628

Citations 23

Authors

Kelly G Matz

Regina P Mtei

Belinda Leung

Sharon J Nieter Burgmayer

Martin L Kirk

Affiliations

Soon will be listed here.

Abstract

A new monoanionic dithiolene ligand is found in Tp*MoO(S(2)BMOQO). A combination of X-ray crystallography, electronic absorption spectroscopy, resonance Raman spectroscopy, and bonding calculations reveal that the monoanionic dithiolene ligand possesses considerable thiolate-thione character resulting from an admixture of an intraligand charge transfer excited state into the ground state wave function. The unusual dithiolene exhibits a highly versatile donor-acceptor character that dramatically affects the Mo(IV/V) redox couple and points to a potentially noninnocent role of the pterin fragment in pyranopterin Mo enzymes.

Citing Articles

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Germaine I, Richey N, Huttel M, McElwee-White L J Mater Chem C Mater. 2024; 12(10):3526-3534.

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Advancing Our Understanding of Pyranopterin-Dithiolene Contributions to Moco Enzyme Catalysis.

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Protonation and Non-Innocent Ligand Behavior in Pyranopterin Dithiolene Molybdenum Complexes.

Gates C, Varnum H, Getty C, Loui N, Chen J, Kirk M Inorg Chem. 2022; 61(35):13728-13742.

PMID: 36000991 PMC: 10544801. DOI: 10.1021/acs.inorgchem.2c01234.

Resonance Raman spectroscopy of pyranopterin molybdenum enzymes.

Kirk M, Lepluart J, Yang J J Inorg Biochem. 2022; 235:111907.

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