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Theoretical investigation into the mechanism of 3'-dGMP oxidation by [PtIVCl4(dach)]
Citation
Ariafard, A and Ghohe, NM and Abbasi, KK and Canty, AJ and Yates, BF, Theoretical investigation into the mechanism of 3'-dGMP oxidation by [PtIVCl4(dach)], Inorganic Chemistry, 52, (2) pp. 707-717. ISSN 0020-1669 (2013) [Refereed Article]
Copyright Statement
Copyright 2012 American Chemical Society
Abstract
The mechanism for the oxidation of 3'-dGMP by [PtCl4(dach)] (dach = diaminocyclohexane) in the presence of [PtCl2(dach)] has been investigated using density functional theory. We find that the initial complexation, i.e., the formation of [PtCl3(dach)(3'-dGMP)], is greatly assisted by the reaction of the encounter pair [PtCl2(dach)···3'-dGMP] with [PtCl4(dach)], leading to migration of an axial chlorine ligand from platinum(IV) to platinum(II). A dinuclear platinum(II)/platinum(IV) intermediate could not be found, but the reaction is predicted to pass through a platinum(III)/platinum(III) transition structure. A cyclization process, i.e., C8-O bond formation, from [PtCl3(dach)(3'-dGMP)] occurs through an intriguing phosphate-water-assisted deprotonation reaction, analogous to the opposite of a proton shuttle mechanism. Followed by this, the guanine moiety is oxidized via dissociation of the PtIV-Clax bond, and the cyclic ether product is finally formed after deprotonation. We have provided rationalizations, including molecular orbital explanations, for the key steps in the process. Our results help to explain the effect of [PtCl4(dach)] on the complexation step and the effect of a strong hydroxide base on the cyclization reaction. The overall reaction cycle is intricate and involves autocatalysis by a platinum(II) species.
Item Details
Item Type: | Refereed Article |
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Research Division: | Chemical Sciences |
Research Group: | Inorganic chemistry |
Research Field: | Bioinorganic chemistry |
Objective Division: | Expanding Knowledge |
Objective Group: | Expanding knowledge |
Objective Field: | Expanding knowledge in the chemical sciences |
UTAS Author: | Ariafard, A (Associate Professor Alireza Ariafard) |
UTAS Author: | Canty, AJ (Professor Allan Canty) |
UTAS Author: | Yates, BF (Professor Brian Yates) |
ID Code: | 88259 |
Year Published: | 2013 |
Web of Science® Times Cited: | 28 |
Deposited By: | Chemistry |
Deposited On: | 2014-01-23 |
Last Modified: | 2017-10-25 |
Downloads: | 0 |
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