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

Ma, Hairong and Wan, Chaozhi and Zewail, Ahmed H. (2008) 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, 105 (35). pp. 12754-12757. ISSN 0027-8424. PMCID PMC2522261. https://resolver.caltech.edu/CaltechAUTHORS:MAHpnas08

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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.


Item Type:Article
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http://dx.doi.org/10.1073/pnas.0806869105DOIArticle
http://www.pnas.org/content/105/35/12754.longPublisherArticle
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2522261/PubMed CentralArticle
Additional Information:© 2008 by The National Academy of Sciences of the USA. Freely available online through the PNAS open access option. Contributed by Ahmed H. Zewail, July 15, 2008 (sent for review June 15, 2008). Published online before print August 25, 2008, doi: 10.1073/pnas.0806869105. This work was supported by the National Science Foundation. Author contributions: H.M., C.W., and A.H.Z. performed research; and H.M. and A.H.Z. wrote the paper. The authors declare no conflict of interest.
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Issue or Number:35
PubMed Central ID:PMC2522261
Record Number:CaltechAUTHORS:MAHpnas08
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:MAHpnas08
Official Citation:Hairong Ma, Chaozhi Wan, and Ahmed H. Zewail Dynamics of ligand substitution in labile cobalt complexes resolved by ultrafast T-jump PNAS 2008 105 (35) 12754-12757; published ahead of print August 25, 2008, doi:10.1073/pnas.0806869105
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11532
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:31 Aug 2008 06:35
Last Modified:03 Oct 2019 00:20

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