Computational design of Oligo-sulfuranes

Priyakumari, Chakkingal P and Jemmis, Eluvathingal D (2016) Computational design of Oligo-sulfuranes. In: JOURNAL OF CHEMICAL SCIENCES, 128 (10). pp. 1663-1669.

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Abstract

We studied the effect of electronegativity perturbation on the isolobal behavior of tetra-coordinate hypervalent compounds of S (sulfuranes, SL (4), L is any atom or group which can provide one electron for S-L bonding). Though formally the fragment SL (4) obtained from SL (6) is an isolobal equivalent of CH (2), a qualitative molecular orbital study shows that only SF (2) H (2) with equatorial F atoms is a practical isolobal substitute for CH (2) and can form oligomers, (SF (2) H (2)) (2), (14), (SF (2) H (2)) (3), (15) and (SF (2) H (2)) (4), (16) analogous to ethylene, cyclopropane and cyclobutane, respectively. DFT computations at the B2PLYP/6-311 ++g(d,p), MP2/aug-cc-pVTZ and B3LYP/6-311 ++g(d,p) levels confirm these structures to be minima on the PES. The skeletal S-S bonds in these structures are formed solely by the bonding combination of anti-bonding fragment orbitals of SF (2) H (2). In contrast, per-fluorination, the usual way to stabilize hypervalent structures, is found to have an opposite effect here. Calculations at the same levels show (SF (4)) (2), (SF (4)) (3), and (SF (4)) (4) not to be minima. The highly stable HOMO of SF (4) fragment and large HOMO-LUMO gap makes SF (4) a stable entity, preventing it from oligomerization. Out of the various isomers of SF (n) H (4-n), n = 0-4, only SF (2) H (2) with equatorial F atoms can form oligomeric sulfuranes. Substitution of F by heavier analogs of the group did not lead to any stable oligomers.

Item Type:	Journal Article
Publication:	JOURNAL OF CHEMICAL SCIENCES
Additional Information:	Copy right for this article belongs to the INDIAN ACAD SCIENCES, C V RAMAN AVENUE, SADASHIVANAGAR, P B #8005, BANGALORE 560 080, INDIA
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	07 Dec 2016 05:08
Last Modified:	07 Dec 2016 05:08
URI:	http://eprints.iisc.ac.in/id/eprint/55482

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