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Analogy between sulfuryl and phosphino groups: the aromaticity of thiophene-oxide

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Abstract

Sulfur in thiophene-oxide is pyramidal, thus this heterocycle shows structural similarities with phosphole. The aromaticity measures (e.g., ISEc = 1.1 kcal/mol; NICS(0) = −5.2) are also comparable (for phosphole ISEc = −2.7 kcal/mol; NICS(0) = −5.4) indicating a borderline non-aromatic/slightly aromatic behavior. The extent of aromaticity is also similar—and high—for the planar transition structures of the inversion motion (thiophene-oxide: ISEc = −20.4 kcal/mol; NICS(0) = −18.7 and phosphole ISEc = −17.7 kcal/mol; NICS(0) = −16.2). This behavior can be rationalized considering the ylidic description of the sulfuryl bond, where the sulfur atom carries a positive charge, which makes it isoelectronic with phosphorus. The similar inversion barriers of the corresponding XH3 (X = N, P, As) and H2Y=O (Y = O, S, Se) species also support this analogy. While no substituents were found, which would make planar thiophene-oxide a viable synthetic target, a planar six-membered heterocycle containing a boron and a sulfuryl unit is suggested for synthetic realization.

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Acknowledgment

Financial support from New Szechenyi PlanTAMOP-4.2.2/B-10/1-2010-0009 is gratefully acknowledged.

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  1. Department of Inorganic and Analytical Chemistry and Materials Structure and Modeling Research Group of the Hungarian Academy of Sciences, Budapest University of Technology and Economics, Szt. Gellért tér 4, Budapest, 1111, Hungary

    Oldamur Hollóczki & László Nyulászi

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  1. Oldamur Hollóczki
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  2. László Nyulászi
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Correspondence to László Nyulászi.

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Hollóczki, O., Nyulászi, L. Analogy between sulfuryl and phosphino groups: the aromaticity of thiophene-oxide. Struct Chem 22, 1385–1392 (2011). https://doi.org/10.1007/s11224-011-9834-8

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