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Synthesis, properties and bishomoaromaticity of the first tetrahalogenated derivative of a 1,5- diphosphadithiatetrazocine: a combined experimental and computational investigation

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dc.contributor.authorChivers, Tristram
dc.contributor.authorHilts, Robert
dc.contributor.authorJin, Peng
dc.contributor.authorChen, Zhongfang
dc.contributor.authorLu, Xin
dc.date.accessioned2022-05-27T01:13:54Z
dc.date.available2022-05-27T01:13:54Z
dc.date.issued2010
dc.description.abstractThe first example of a tetrahalogenated derivative of a diphosphadithiatetrazocine, 1,5-Cl2P(NSN)2PCl2 (3), was synthesized by cyclocondensation of a 2:1 mixture of SCl2 and SO2Cl2 with Cl2P(NSiMe3)N(SiMe3)2 in CH2Cl2. The heterocycle 3 was isolated as an orange, moisture-sensitive, thermally labile solid and characterized by mass spectrometry, 31P NMR, and UV−visible spectroscopy. The low-field 31P NMR chemical shift (93.7 ppm) is indicative of a cross-ring S---S interaction in the eight-membered P2N4S2 ring, and this conclusion is supported by density-functional computations. Compound 3 exhibits unusual physical properties compared with those of the known tetraalkyl or aryl derivatives; mild heating (90 °C) produces an orange rubbery material. The bishomoaromatic character of the diphosphadithiatetrazocine 1,5-R2P(NSN)2PR2 (R = Me, Cl, F) is evinced by the negative nucleus-independent chemical shift (NICS) values, and the through-space bishomoconjugation in the eight-membered ring decreases with increasing electronegativity of the substituents attached to the P atoms.
dc.description.urihttp://library.macewan.ca/cgi-bin/SFX/url.pl/7OW
dc.identifier.citationChivers, T., Hilts, R. W., Peng Jin, Zhongfang Chen, & Xin Lu. (2010). Synthesis, Properties, and Bishomoaromaticity of the First Tetrahalogenated Derivative of a 1, 5-Diphosphadithiatetrazocine: A Combined Experimental and Computational Investigation. Inorganic Chemistry, 49(8), 3810–3815. https://doi.org./10.1021/ic902428j
dc.identifier.doihttps://doi.org./10.1021/ic902428j
dc.identifier.urihttps://hdl.handle.net/20.500.14078/312
dc.languageEnglish
dc.language.isoen
dc.rightsAll Rights Reserved
dc.subjectsynthesis
dc.subjectbishomoaromaticity
dc.subjectcomputational investigation
dc.titleSynthesis, properties and bishomoaromaticity of the first tetrahalogenated derivative of a 1,5- diphosphadithiatetrazocine: a combined experimental and computational investigationen
dc.typeArticle

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Department of Physical Sciences