Dynamics of ligand substitution in labile cobalt complexes resolved by ultrafast T-jump.

Proceedings of the National Academy of Sciences of the United States of America
Hairong MaA H Zewail

Abstract

Ligand exchange of hydrated metal complexes is common in chemical and biological systems. Using the ultrafast T-jump, we examined this process, specifically the transformation of aqua cobalt (II) complexes to their fully halogenated species. The results reveal a stepwise mechanism with time scales varying from hundreds of picoseconds to nanoseconds. The dynamics are significantly faster when the structure is retained but becomes rate-limited when the octahedral-to-tetrahedral structural change bottlenecks the transformation. Evidence is presented, from bimolecular kinetics and energetics (enthalpic and entropic), for a reaction in which the ligand assists the displacement of water molecules, with the retention of the entering ligand in the activated state. The reaction time scale deviates by one to two orders of magnitude from that of ionic diffusion, suggesting the involvement of a collisional barrier between the ion and the much larger complex.

References

Mar 27, 2003·Proceedings of the National Academy of Sciences of the United States of America·Harry B Gray
Dec 17, 2004·Proceedings of the National Academy of Sciences of the United States of America·Yuhong WangAhmed H Zewail
Jan 27, 2005·Journal of the American Chemical Society·Preston T SneeCharles B Harris
Jun 9, 2005·Chemical Reviews·David T Richens
May 11, 2006·Journal of the American Chemical Society·Hairong MaAhmed H Zewail
Jan 12, 2007·Proceedings of the National Academy of Sciences of the United States of America·Hairong MaAhmed H Zewail

❮ Previous
Next ❯

Citations

Oct 11, 2011·Inorganic Chemistry·Theresa M McCormickRichard Eisenberg
Feb 26, 2016·Inorganic Chemistry·Stefanie Martina MunzertDirk G Kurth
Jun 17, 2015·The Journal of Physical Chemistry. B·Andrey S MereshchenkoAlexander N Tarnovsky
Jun 5, 2013·Chemistry : a European Journal·Mirco NataliFranco Scandola
Jan 23, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·S S AnjanaNarasimha N Murthy
Nov 2, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Paola A BenavidesKoiti Araki
Dec 14, 2019·Structural Dynamics·O CannelliM Chergui
Apr 23, 2021·Physical Chemistry Chemical Physics : PCCP·Marwah M M MadkhaliThomas J Penfold
May 23, 2015·The Journal of Physical Chemistry. B·Pankaj Kr MishraRobin Santra
Apr 10, 2013·The Journal of Physical Chemistry. B·Guihua WangXiyun Guan
Nov 30, 2011·The Journal of Physical Chemistry. a·Andrey S MereshchenkoAlexander N Tarnovsky
May 20, 2018·The Journal of Physical Chemistry. a·Pankaj Kr MishraRalph Welsch

❮ 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.