Source:http://linkedlifedata.com/resource/pubmed/id/11327894
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rdf:type | |
lifeskim:mentions | |
pubmed:issue |
10
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pubmed:dateCreated |
2001-4-30
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pubmed:abstractText |
A kinetic study of the reaction between a diiron(II) complex [Fe(II)(2)(mu-OH)(2)(6-Me(3)-TPA)(2)](2+) 1, where 6-Me(3)-TPA = tris(6-methyl-2-pyridylmethyl)amine, and dioxygen is presented. A diiron(III) peroxo complex [Fe(III)(2)(mu-O)(mu-O(2))(6-Me(3)-TPA)(2)](2+) 2 forms quantitatively in dichloromethane at temperatures from -80 to -40 degrees C. The reaction is first order in [Fe(II)(2)] and [O(2)], with the activation parameters DeltaH(double dagger) = 17 +/- 2 kJ mol(-1) and DeltaS(double dagger) = -175 +/- 20 J mol(-1) K(-1). The reaction rate is not significantly influenced by the addition of H(2)O or D(2)O. The reaction proceeds faster in more polar solvents (acetone and acetonitrile), but the yield of 2 is not quantitative in these solvents. Complex 1 reacts with NO at a rate about 10(3) faster than with O(2). The mechanistic analysis suggests an associative rate-limiting step for the oxygenation of 1, similar to that for stearoyl-ACP Delta(9)-desaturase, but distinct from the probable dissociative pathway of methane monoxygenase. An eta(1)-superoxo Fe(II)Fe(III) species is a likely steady-state intermediate during the oxygenation of complex 1.
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pubmed:grant | |
pubmed:language |
eng
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pubmed:journal | |
pubmed:citationSubset |
IM
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pubmed:chemical | |
pubmed:status |
MEDLINE
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pubmed:month |
May
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pubmed:issn |
0020-1669
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pubmed:author | |
pubmed:issnType |
Print
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pubmed:day |
7
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pubmed:volume |
40
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
2220-8
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pubmed:dateRevised |
2007-11-14
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pubmed:meshHeading | |
pubmed:year |
2001
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pubmed:articleTitle |
A mechanistic study of the reaction between a diiron(II) complex [FeII(2)(mu-OH)2(6-Me3-TPA)2](2+) and O2 to form a diiron(III) peroxo complex.
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pubmed:affiliation |
Department of Chemistry, Tufts University, Medford, MA 02155, USA.
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pubmed:publicationType |
Journal Article,
Research Support, U.S. Gov't, P.H.S.,
Research Support, Non-U.S. Gov't
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