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

Chivers, T., Hilts, R., Jin, P., Chen, Z., & Lu, X. (2010). Synthesis, properties and bishomoaromaticity of the first tetrahalogenated derivative of a 1,5- diphosphadithiatetrazocine: a combined experimental and computational investigation.
Metadata
TitleSynthesis, properties and bishomoaromaticity of the first tetrahalogenated derivative of a 1,5- diphosphadithiatetrazocine: a combined experimental and computational investigation
Author(s)Chivers, Tristram; Hilts, Robert; Jin, Peng; Chen, Zhongfang; Lu, Xin
Date2010
Keyword(s)synthesis, bishomoaromaticity, computational investigation
DescriptionThe 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.
Peer ReviewedYes
Type of ItemJournal Articles
MacEwan Users Onlyhttp://library.macewan.ca/cgi-bin/SFX/url.pl/7OW
LanguageEnglish
RightsAll Rights Reserved