Universität zu Köln

Holloczki, Oldamur ORCID: 0000-0003-3105-7176, Berkessel, Albrecht ORCID: 0000-0003-0470-7428, Mars, Julian ORCID: 0000-0003-0557-2983, Mezger, Markus ORCID: 0000-0001-9049-6983, Wiebe, Anton, Waldvogel, Siegfried R. ORCID: 0000-0002-7949-9638 and Kirchner, Barbara ORCID: 0000-0001-8843-7132 (2017). The Catalytic Effect of Fluoroalcohol Mixtures Depends on Domain Formation. ACS Catal., 7 (3). S. 1846 - 1853. WASHINGTON: AMER CHEMICAL SOC. ISSN 2155-5435

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Abstract

In the present contribution, we investigated catalytically active mixtures of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and aqueous H2O2 by molecular dynamics simulations. It is clearly observable that the HFIP molecule strongly binds to the H2O2, which is necessary for the desired catalytic reaction to occur. Upon the addition of the substrate cyclooctene to the solution, this interaction is enhanced, which suggests that the catalytic activity is increased by the presence of the hydrocarbon. We could clearly observe the microheterogeneous structure of the mixture, which is the result of the separation of the hydroxyl groups, water, and H2O2 from the fluorinated alkyl moiety in the form of large domains, which span through large areas of the system. The hydrocarbon, however, does not fit into either one of these two microphases, and it forms separate aggregates in the macroscopically homogeneous liquid, creating thereby a triphilic mixture. The latter kinds of aggregates are mostly surrounded by the fluorous moieties, and therefore, the H2O2 has to move from the polar through the fluorous domain to be able to react with the cyclooctene. Accordingly, the present reaction should be described figuratively as a phase transfer or an interfacial reaction, rather than a homogeneous liquid-phase process.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Holloczki, Oldamur UNSPECIFIED orcid.org/0000-0003-3105-7176 UNSPECIFIED Berkessel, Albrecht UNSPECIFIED orcid.org/0000-0003-0470-7428 UNSPECIFIED Mars, Julian UNSPECIFIED orcid.org/0000-0003-0557-2983 UNSPECIFIED Mezger, Markus UNSPECIFIED orcid.org/0000-0001-9049-6983 UNSPECIFIED Wiebe, Anton UNSPECIFIED UNSPECIFIED UNSPECIFIED Waldvogel, Siegfried R. UNSPECIFIED orcid.org/0000-0002-7949-9638 UNSPECIFIED Kirchner, Barbara UNSPECIFIED orcid.org/0000-0001-8843-7132 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-238748
DOI:	10.1021/acscatal.6b03090
Journal or Publication Title:	ACS Catal.
Volume:	7
Number:	3
Page Range:	S. 1846 - 1853
Date:	2017
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	2155-5435
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language MOLECULAR-DYNAMICS; FLUORINATED ALCOHOLS; HYDROGEN-PEROXIDE; OLEFIN EPOXIDATION; CANONICAL ENSEMBLE; SIMULATIONS; 1,1,1,3,3,3-HEXAFLUOROPROPAN-2-OL; ACTIVATION; SOLVENTS; LIQUIDS Multiple languages Chemistry, Physical Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/23874