Universität zu Köln

Breugst, Martin ORCID: 0000-0003-0950-8858, Detmar, Eric and von der Heiden, Daniel (2016). Origin of the Catalytic Effects of Molecular Iodine: A Computational Analysis. ACS Catal., 6 (5). S. 3203 - 3213. WASHINGTON: AMER CHEMICAL SOC. ISSN 2155-5435

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Abstract

Molecular iodine is an excellent catalyst for many organic transformations, but the origin of its catalytic activity is still unknown. To answer this question, we have analyzed four iodine-catalyzed reactions by density functional theory. Our calculations reveal that molecular iodine significantly reduces the activation free energies (-7.6 < Delta G(double dagger) < -1.8 kcal mol(-1)) for reactions involving alpha,beta-unsaturated carbonyls or nitrostyrenes. Closer analysis of the nature of the interaction between iodine and the corresponding Michael acceptors suggests that halogen bonding is the origin of the catalytic activity. The computational and experimental studies show that hidden Bronsted acid catalysis as a competing pathway due to the formation of hydrogen iodide via hypoiodites in aprotic solvents seems less likely for these reactions.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Breugst, Martin UNSPECIFIED orcid.org/0000-0003-0950-8858 UNSPECIFIED Detmar, Eric UNSPECIFIED UNSPECIFIED UNSPECIFIED von der Heiden, Daniel UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-277468
DOI:	10.1021/acscatal.6b00447
Journal or Publication Title:	ACS Catal.
Volume:	6
Number:	5
Page Range:	S. 3203 - 3213
Date:	2016
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 HYBRID DENSITY FUNCTIONALS; HALOGEN-BOND; MICHAEL ADDITION; BASICITY; COMPOUND; PROGRAM; KETONES; ENERGY Multiple languages Chemistry, Physical Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/27746