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Theoretical investi...
Theoretical investigation on the oxidative chlorination performed by a biomimetic non-heme iron catalyst
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- Noack, Holger (författare)
- Stockholms universitet,Fysikum,Per E.M. Siegbahn, Margareta R.A. Blomberg
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- Siegbahn, Per E. M. (författare)
- Stockholms universitet,Fysikum,Per E.M. Siegbahn, Margareta R.A. Blomberg
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(creator_code:org_t)
- 2007
- 2007
- Engelska.
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Ingår i: Journal of Biological Inorganic Chemistry. - 0949-8257 .- 1432-1327. ; 12, s. 1151-1162
- Relaterad länk:
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http://www04.sub.su....
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Abstract
Ämnesord
Stäng
- The present study is a part of an effort to understand the mechanism of the oxidative chlorination, as performed by a biomimetic non-heme iron complex. This catalytically active complex is generated from a peroxide and [(TPA)FeIIICl2]+ [TPA is tris(2-pyridylmethyl)amine]. The reaction catalyzed by [(TPA)FeCl2]+/ROOH involves either [(TPA)ClFeV=O]2+ or [(TPA)ClFeIV=O]+ as an intermediate. On the basis of density functional theory the reaction of these two possible catalysts with cyclohexane is investigated. A question addressed is how the competing hydroxylation of the substrate is avoided. It is demon- strated that the high-valent iron complex [(TPA)Cl– FeV=O]2+ is capable of stereospecific alkane chlorination, based on an ionic rather than on a radical pathway. In contrast, the results found for [(TPA)ClFeIV=O]+ cannot explain the experimental findings. In this case the transition states for chlorination and hydroxylation are energetically too close. The exclusive chlorination of the substrate by Cl–FeIV=O may be explained by an indirect or a direct effect, altering the position of the competing rebound barriers.
Ämnesord
- NATURVETENSKAP -- Kemi -- Fysikalisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Physical Chemistry (hsv//eng)
Nyckelord
- Halogenation iron biomimetic dft chlorination non-heme
- Physical chemistry
- Fysikalisk kemi
Publikations- och innehållstyp
- ref (ämneskategori)
- art (ämneskategori)
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