Universität zu Köln

Juanes, Marcos, Saragi, Rizalina Tama, Zingsheim, Oliver, Schlemmer, Stephan and Lesarri, Alberto (2021). Chirality, structure and hydrogen bonding in dithiols: Rotational spectrum of the chiral and meso 2,3-butanedithiol. J. Mol. Struct., 1246. AMSTERDAM: ELSEVIER. ISSN 1872-8014

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Abstract

We have characterized the homochiral (2R, 3R) and heterochiral meso (2R,3S) isomers of 2,3-butanedithiol, using rotational spectroscopy at centimeter and millimeter-wave frequencies. The microwave experiment used jet-cooled chirped-pulsed fast-passage excitation in the range 2-8 GHz, while the millimeter-wave measurements in the regions 75-129 and 170-300 GHz used source modulation and lock-in detection at room temperature. A single rotamer was observed for each structural isomer, more intense for the homochiral species. The homochiral carbon skeleton is antiperiplanar and differs from the synclinal skeleton of the heterochiral isomer. However, the two rotamers share synclinal sulfur atoms which permit S-H center dot center dot center dot S intramolecular hydrogen bonds, illustrating chirality-dependent synchronization. Density functional theory methods (B3LYP and B2PLYP) with (D3) dispersion corrections complemented the experimental work. Additionally, the presence of intramolecular interactions was assessed with an analysis of the reduced electronic density gradient with the NCIPlot method, which suggested both S-H center dot center dot center dot S and weak C-H center dot center dot center dot S interactions. (C) 2021 The Author(s). Published by Elsevier B.V.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Juanes, Marcos UNSPECIFIED UNSPECIFIED UNSPECIFIED Saragi, Rizalina Tama UNSPECIFIED UNSPECIFIED UNSPECIFIED Zingsheim, Oliver UNSPECIFIED UNSPECIFIED UNSPECIFIED Schlemmer, Stephan UNSPECIFIED UNSPECIFIED UNSPECIFIED Lesarri, Alberto UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-574816
DOI:	10.1016/j.molstruc.2021.131221
Journal or Publication Title:	J. Mol. Struct.
Volume:	1246
Date:	2021
Publisher:	ELSEVIER
Place of Publication:	AMSTERDAM
ISSN:	1872-8014
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language MICROWAVE-SPECTRUM; CONFORMATIONAL PROPERTIES; WAVE SPECTROSCOPY; DIPOLE-MOMENT; ETHANETHIOL; MERCAPTAN Multiple languages Chemistry, Physical Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/57481