A1 Refereed original research article in a scientific journal
Cleavage and isomerization of UpU promoted by dinuclear metal ion complexes
Authors: Linjalahti H, Feng GQ, Mareque-Rivas JC, Mikkola S, Williams NH
Publisher: AMER CHEMICAL SOC
Publication year: 2008
Journal: Journal of the American Chemical Society
Journal name in source: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Journal acronym: J AM CHEM SOC
Volume: 130
Issue: 13
First page : 4232
Last page: +
Number of pages: 3
ISSN: 0002-7863
DOI: https://doi.org/10.1021/ja711347w
The catalysis of phosphoryl transfer by metal ions has been intensively studied in both biological and artificial systems, but the status of the transient pentacoordinate phosphoryl species (as transition state or intermediate) is the subject of considerable debate. We report that dinuclear metal ion complexes that incorporate second sphere hydrogen bond donors not only promote the cleavage of RNA fragments just as efficiently as the activated analogue HPNPP but also provide the first examples of metal ion catalyzed phosphate diester isomerization close to neutral pH. This observation implies that the reaction catalyzed by these complexes involves the formation of a phosphorane intermediate that is sufficiently long-lived to pseudorotate.