Source:http://linkedlifedata.com/resource/pubmed/id/15651877
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| Predicate | Object |
|---|---|
| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
2
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| pubmed:dateCreated |
2005-1-17
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| pubmed:abstractText |
The acidity (pull) and the axial ligand (push) effects on the O-O bond cleavage in the [(Salen)Mn(III)(RCO(3))L] acylperoxo complexes, with model L = none, NH(3), and HCO(2)(-) (1), have been studied with B3LYP density functional calculations. The acidic conditions have been mimicked by explicit protonation of 1 to afford a variety of [(Salen)Mn(III)(RCO(3)H)L] (2) and [(SalenH)Mn(III)(RCO(3))L] (3) complexes in ground quintet states. The protonation assists the O-O bond heterolysis, thus primarily forming highly reactive Mn(V)(O) species, and consequently suppresses formation of the less reactive Mn(IV)(O) species through homolytic channel described earlier in 1 [Khavrutskii, I. V.; Rahim, R. R.; Musaev, D. G.; Morokuma, K. J. Phys. Chem. B 2004, 108, 3845-3854]. In addition to the qualitative change of the O-O bond cleavage mode, the protonation affects the rate of the O-O bond cleavage. Therefore, varying the acidity of the reaction media helps control the O-O bond cleavage mode and rate.
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:month |
Jan
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| pubmed:issn |
0020-1669
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| pubmed:author | |
| pubmed:issnType |
Print
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| pubmed:day |
24
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| pubmed:volume |
44
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| pubmed:owner |
NLM
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| pubmed:authorsComplete |
Y
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| pubmed:pagination |
306-15
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| pubmed:year |
2005
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| pubmed:articleTitle |
Cooperative pull and push effects on the O-O bond cleavage in acylperoxo complexes of [(Salen)MnIIIL]: ensuring formation of manganese(V) oxo species.
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| pubmed:affiliation |
Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
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| pubmed:publicationType |
Journal Article
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