Deprotonation of Water Ligands in V, Cr, Mn, Fe, and Co Complexes Reduces Oxidation-Driven Carboxylate Ligand Frequency Shifts

The Journal of Physical Chemistry. B
Wooi Yee Chuah, Terry J Frankcombe

Abstract

In Mn complexes, it has been shown that oxidation-driven changes in carboxylate ligand vibrations are suppressed, if a water or hydroxo ligand is simultaneously deprotonated. Deprotonation with oxidation has also been shown to greatly reduce the dependence of Mn complex redox energies on the oxidation state of the metal. We have here investigated the effect of oxidation with deprotonation on the carboxylate ligand frequencies of V, Cr, Mn, Fe, and Co complexes. The effects of anionic ligand substitution (instead of deprotonation) and solvent dielectric were also investigated to determine the mechanism that drives carboxylate frequency shifts. It is shown that the effect of deprotonation was similar for all of the metals tested in this study. C-O bond lengths and O-C-O angle changes in the carboxylate ligand were also reduced by deprotonation. Furthermore, the effect of anionic ligand substitution was similar to deprotonation in the suppression of carboxylate frequency shifts. These shifts were also reduced by increases in the solvent dielectric, in the absence of charge conservation through deprotonation. Therefore, we conclude that carboxylate frequency shifts are largely driven by electrostatic effects.

References

Mar 14, 2002·Journal of the American Chemical Society·Edit Y TshuvaStephen J Lippard
Feb 12, 2004·Chemical Reviews·Edit Y Tshuva, Stephen J Lippard
Mar 2, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Gerriet EilersReiner Lomoth
Jul 11, 2006·Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy·V ZelenákK Györyová
May 23, 2008·Coordination Chemistry Reviews·Richard J Debus
Dec 22, 2009·Chemical Society Reviews·Joshua P Abell, Hisashi Yamamoto
Jan 2, 2010·Carbohydrate Research·Sergios K PapageorgiouFotios K Katsaros
Mar 25, 2010·The Journal of Chemical Physics·Giovanni Scalmani, Michael J Frisch
Nov 26, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Cécile MarieKenneth L Nash
Mar 27, 2013·Annual Review of Biochemistry·David J VinyardG Charles Dismukes
Mar 13, 2014·The Journal of Physical Chemistry. B·Wooi Yee ChuahTerry J Frankcombe

❮ Previous
Next ❯

Citations

Jul 24, 2021·Inorganic Chemistry·Meiling LiQinhe Pan

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.