Universität zu Köln

Detmar, Eric, Mueller, Valentin, Zell, Daniel, Ackermann, Lutz and Breugst, Martin ORCID: 0000-0003-0950-8858 (2018). Cobalt-catalyzed C-H cyanations: Insights into the reaction mechanism and the role of London dispersion. Beilstein J. Org. Chem., 14. S. 1537 - 1546. FRANKFURT AM MAIN: BEILSTEIN-INSTITUT. ISSN 1860-5397

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Abstract

Carboxylate-assisted cobalt(III)-catalyzed C-H cyanations are highly efficient processes for the synthesis of (hetero) aromatic nitriles. We have now analyzed the cyanation of differently substituted 2-phenylpyridines in detail computationally by density functional theory and also experimentally. Based on our investigations, we propose a plausible reaction mechanism for this transformation that is in line with the experimental observations. Additional calculations, including NCIPLOT, dispersion interaction densities, and local energy decomposition analysis, for the model cyanation of 2-phenylpyridine furthermore highlight that London dispersion is an important factor that enables this challenging C-H transformation. Nonbonding interactions between the Cp* ligand and aromatic and C-H-rich fragments of other ligands at the cobalt center significantly contribute to a stabilization of cobalt intermediates and transition states.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Detmar, Eric UNSPECIFIED UNSPECIFIED UNSPECIFIED Mueller, Valentin UNSPECIFIED UNSPECIFIED UNSPECIFIED Zell, Daniel UNSPECIFIED UNSPECIFIED UNSPECIFIED Ackermann, Lutz UNSPECIFIED UNSPECIFIED UNSPECIFIED Breugst, Martin UNSPECIFIED orcid.org/0000-0003-0950-8858 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-182619
DOI:	10.3762/bjoc.14.130
Journal or Publication Title:	Beilstein J. Org. Chem.
Volume:	14
Page Range:	S. 1537 - 1546
Date:	2018
Publisher:	BEILSTEIN-INSTITUT
Place of Publication:	FRANKFURT AM MAIN
ISSN:	1860-5397
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 DENSITY-FUNCTIONAL THEORY; ORBITAL COUPLED-CLUSTER; CARBON-CARBON BONDS; BASIS-SETS; THERMOCHEMISTRY; ACTIVATION; CHEMISTRY; PROGRAM; ARYLATIONS; PRELIGANDS Multiple languages Chemistry, Organic Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/18261