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Modeling water exchange on monomeric and dimeric Mn centers
Department of Physics, Stockholm Center for Physics, Astronomy and Biotechnology, Stockholm University.
2003 (English)In: Theoretical Chemistry accounts, ISSN 1432-881X, E-ISSN 1432-2234, Vol. 110, no 3, 130-143 p.Article in journal (Refereed) Published
Abstract [en]

Water exchange on Mn centers in proteins has been modeled with density functional theory using the B3LYP functional. The reaction barrier for dissociative water exchange on [Mn-IV(H2O)(2)(OH)(4)] is only 9.6 kcal mol(-1), corresponding to a rate of 6 x 10(5) s(-1). It has also been investigated how modifications of the model complex change the exchange rate. Three cases of water exchange on Mn dimers have been modeled. The reaction barrier for dissociative exchange of a terminal water ligand on [(H2O)(2)(OH)(2)Mn-IV(mu-O)(2)Mn-IV(H2O)(2) (OH)(2)] is 8.6 kcal mol(-1), while the bridging oxo group exchange with a ring-opening mechanism has a barrier of 19.2 kcal mol(-1). These results are intended for interpretations of measurements of water exchange for the oxygen evolving complex of photosystem II. Finally, a tautomerization mechanism for exchange of a terminal oxyl radical has been modeled for the synthetic 02 catalyst [(terpy)(H2O)Mn-IV(mu-O)(2)Mn-IV(O.)(terpy)](3+) (terpy=2,2':6,2"-terpyridine). The calculated reaction barrier is 14.7 kcal mol(-1).

Place, publisher, year, edition, pages
2003. Vol. 110, no 3, 130-143 p.
Keyword [en]
water exchange, manganese, dimers, density functional theory
National Category
Natural Sciences
URN: urn:nbn:se:uu:diva-145462DOI: 10.1007/s00214-003-0474-yOAI: oai:DiVA.org:uu-145462DiVA: diva2:396526
Available from: 2011-02-10 Created: 2011-02-09 Last updated: 2016-04-22

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Lundberg, Marcus
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