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Computational design of Oligo-sulfuranes

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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.

SF2H2 with equatorial F atoms is isolobal to CH2 and forms the oligomers (SF2H2)2, (SF2H2)3, and (SF2H2)4 analogous to ethylene, cyclopropane and cyclobutane, respectively. The skeletal S-S bonds are formed by the overlap of antibonding fragment orbitals of SF2H2.

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Acknowledgements

CPK and EDJ thank IISER Thiruvananthapuram, IISc Bangalore and CMSD, University of Hyderabad for providing computational facilities. CPK thanks CSIR-India for research fellowship. DST is acknowledged for the J C Bose fellowship to EDJ.

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Authors and Affiliations

  1. School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, CET Campus, Thiruvananthapuram, Kerala, 695 016, India

    CHAKKINGAL P PRIYAKUMARI

  2. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, Karnataka, 560 012, India

    ELUVATHINGAL D JEMMIS

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  1. CHAKKINGAL P PRIYAKUMARI
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Correspondence to ELUVATHINGAL D JEMMIS.

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Supplementary Information (SI)

Coordinates of the structures are given in the Supporting Information, available at www.ias.ac.in/chemsci.

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PRIYAKUMARI, C.P., JEMMIS, E.D. Computational design of Oligo-sulfuranes. J Chem Sci 128, 1663–1669 (2016). https://doi.org/10.1007/s12039-016-1157-2

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