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Dynamic Covalent Chemistry under High‐Pressure:A New Route to Disulfide Metathesis
Author(s) -
Sobczak Szymon,
Drożdż Wojciech,
Lampronti Giulio I.,
Belenguer Ana M.,
Katrusiak Andrzej,
Stefankiewicz Artur R.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201801740
Subject(s) - metathesis , chemistry , dynamic covalent chemistry , disulfide bond , grinding , salt metathesis reaction , mechanochemistry , phase transition , covalent bond , supercritical fluid , ball mill , catalysis , high pressure , crystallography , chemical engineering , organic chemistry , crystal structure , materials science , thermodynamics , polymerization , metallurgy , biochemistry , supramolecular chemistry , physics , engineering , polymer
This work describes, for the first time, the application of combined pressure and temperature stimuli in disulfide metathesis reactions. In the system studied, above a pressure of 0.2 GPa, equimolar amounts of symmetric disulfides bis 4‐chlorophenyl disulfide [(4‐ClPhS) 2 ] and bis 2‐nitrophenyl disulfide [(2‐NO 2 PhS) 2 ] react to give the heterodimeric product 4‐Cl‐PhSSPh‐2‐NO 2 . In contrast to experiments conducted in solution at atmospheric pressure or in mechanochemical experiments under ball‐mill grinding conditions, there is no necessity to use a base or thiolate anion as a catalyst for the exchange reaction under investigated conditions. Single‐crystal and powder X‐ray diffraction revealed also that, despite the high‐pressure conditions of this reaction, the heterodimeric‐disulfide product unexpectedly crystallizes into the low‐density polymorph A. This counterintuitive result contrasts with the high‐pressure stability of the higher‐density polymorph B, confirmed by its compression up to 2.8 GPa with no signs of a phase transition.