Electrocatalytic proton reduction by phosphido-bridged diiron carbonyl compounds: distant relations to the H-cluster?

Inorganic Chemistry
Mun Hon CheahStephen P Best

Abstract

Intermediates formed during reduction of Fe(2)(mu-PPh(2))(2)(CO)(6) (1) in the presence of protons have been identified by spectroelectrochemical, continuous-flow, and interrupted-flow techniques. The mechanism for electrocatalytic proton reduction suggested by these observations yields digital simulation of the voltammetry in close agreement with measurements conducted in THF over a range of acid concentrations. The mechanism for electrocatalytic proton reduction involves initial formation of the dianion, 1(2-), which is doubly protonated prior to further reduction and dihydrogen elimination. The IR spectra of the singly and doubly protonated forms of 1(2-) indicate structures corresponding to [FeH(CO)(3)(mu-PPh(2))(2)Fe(CO)(3)](-) (1H-) and FeH(CO)(3)(mu-PPh(2))(2)FeH(CO)(3) (1H(2)). The thiolato and dithiolato analogues of 1 exhibit electrocatalytic proton reduction associated with the two-electron reduction step, and this implies that the corresponding two-electron reduced doubly protonated species is unstable with respect to dihydrogen elimination. The stability of 1H(2) is most likely to be due to the weak interactions between the iron centers of the flattened [2Fe2P] core. Whereas 1H(2) is stable in the absence of a redu...Continue Reading

References

Dec 4, 1998·Science·L G ThompsonB Francou
Jul 15, 1995·Physical Review. B, Condensed Matter·S I ZabinskyM J Eller
Jun 1, 1993·Physical Review. B, Condensed Matter·M NewvilleE A Stern
Oct 1, 1993·Physical Review. B, Condensed Matter·E A Stern
Dec 10, 2002·Inorganic Chemistry·Frédéric GloaguenMarie-Madeleine Rohmer
Mar 19, 2003·Proceedings of the National Academy of Sciences of the United States of America·Marcetta Y DarensbourgIrene P Georgakaki
Jan 1, 1995·Journal of Synchrotron Radiation·S J Gurman
Jul 1, 1995·Journal of Synchrotron Radiation·P J Ellis, H C Freeman

❮ Previous
Next ❯

Citations

Jun 30, 2016·Chemical Reviews·David SchilterThomas B Rauchfuss
Feb 22, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Ahibur RahamanStephen B Colbran
Oct 13, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Ralf TrautweinWolfgang Weigand
Apr 10, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Shang GaoJun Hou
Dec 18, 2008·Chemical Society Reviews·Frédéric Gloaguen, Thomas B Rauchfuss
Jul 15, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Kinga KaniewskaRafał Grubba
Feb 27, 2007·Angewandte Chemie·Wolfgang Kaim, Goutam Kumar Lahiri
Oct 28, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Takehiko ShimamuraTsutomu Mizuta
Mar 12, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Bryan E BartonScott R Wilson
Dec 12, 2020·Chemical Society Reviews·Julian T KleinhausUlf-Peter Apfel
Mar 2, 2006·Journal of the American Chemical Society·Renee M HenryM Rakowski DuBois
Sep 27, 2007·Journal of the American Chemical Society·Greg A N FeltonDennis L Lichtenberger
Aug 4, 2005·Journal of the American Chemical Society·Christine A BoykeLuca De Gioia
Dec 23, 2004·Journal of the American Chemical Society·Stacey J BorgChristopher J Pickett

❮ 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.