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Sulfur Imide and Derivatives

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S Sulfur-Nitrogen Compounds

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Abstract

S=NH, the parent compound of the sulfur imide compounds, has not yet been isolated in the free state. However, it was possible to stabilize the molecule by coordination as a six-electron ligand to two Fe atoms like in Fe2(CO)6(μ-S=NH) [1]; see p. 2. Several quantum-chemical calculations using semiempirical and ab initio approaches have been performed; see Table 1. According to these studies, S=NH has a closed-shell 11A’ ground state which is 1.02 eV (23.4 kcal/mol) lower than the ground state of the isomer HSEN. There is no low-lying barrier that can allow thermal isomerization [2]. The energy difference between the 11A’ singlet and the 13A“ triplet states of S=NH is very small (42 kJ/mol at the MP2/6-31 G** [3] and 28 kJ/mol at the CEPA-SD level [2]) and classifies the molecule as a biradicaloid species. Optimization of the equilibrium geometry in the ground state showed S=NH to be a bent molecule having an HNS bond angle of 110° (SCF/6-31 G** level) [3] or 107° (CEPA-SD level) [2]. The SN bond length is 1.59 A at CEPA-SD level (N¡ªH = 1.03) [2] and 1.54 A at SCF/6-31 G** level (N-H = 1.01) [3] (corresponding to a conventional SN double bond). The proton affinity was estimated to range from 153 (triplet) to 195 (singlet) kcal/mot at the MP4 level. Protonation at nitrogen is expected to be preferable over protonation at sulfur [4].

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Authors and Affiliations

  1. Frankfurt am Main, Germany

    Alfons Kubny

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  1. Norbert Baumann
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  2. Hans-Jürgen Fachmann
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  3. Reimund Jotter
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    Alfons Kubny

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© 1994 Springer-Verlag Berlin Heidelberg

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Baumann, N., Fachmann, HJ., Jotter, R., Kubny, A. (1994). Sulfur Imide and Derivatives. In: Baumann, N., Fachmann, HJ., Jotter, R., Kubny, A. (eds) S Sulfur-Nitrogen Compounds. Gmelin Handbook of Inorganic and Organometallic Chemistry / Gmelin Handbuch der Anorganischen Chemie, vol S / S-N / 10 / a. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-06351-4_1

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  • DOI: https://doi.org/10.1007/978-3-662-06351-4_1

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