Non-Innocent Base Properties of 3- and 4-Pyridyl-dithia- and Diselenadiazolyl Radicals : The Effect of N-Methylation
Taponen, A., Wong, J. W. L., Lekin, K., Assoud, A., Robertson, C. M., Lahtinen, M., Clérac, R., Tuononen, H., Mailman, A., & Oakley, R. T. (2018). Non-Innocent Base Properties of 3- and 4-Pyridyl-dithia- and Diselenadiazolyl Radicals : The Effect of N-Methylation. Inorganic Chemistry, 57(21), 13901-13911. https://doi.org/10.1021/acs.inorgchem.8b02416
Julkaistu sarjassa
Inorganic ChemistryTekijät
Päivämäärä
2018Tekijänoikeudet
© 2018 American Chemical Society
Condensation of persilylated nicotinimideamide and isonicotinimideamide with sulfur monochloride affords double salts of the 3-, 4-pyridyl-substituted 1,2,3,5-dithiadiazolylium DTDA cations of the general formula [3-, 4-pyDTDA][Cl][HCl] in which the pyridyl nitrogen serves as a noninnocent base. Reduction of these salts with triphenylantimony followed by deprotonation of the intermediate-protonated radical affords the free base radicals [3-, 4-pyDTDA], the crystal structures of which, along with those of their diselenadiazolyl analogues [3-, 4-pyDSDA], have been characterized by powder or single-crystal X-ray diffraction. The crystal structures consist of “pancake” π-dimers linked head-to-tail into ribbonlike arrays by η2-S2---N(py) intermolecular secondary bonding interactions. Methylation of the persilylated (iso)nicotinimide-amides prior to condensation with sulfur monochloride leads to N-methylated double chloride salts Me[3-, 4-pyDTDA][Cl]2, which can be converted by metathesis into the corresponding triflates Me[3-, 4-pyDTDA][OTf]2 and then reduced to the N-methylated radical triflates Me[3-, 4-pyDTDA][OTf]. The crystal structures of both the N-methylated double triflate and radical triflate salts have been determined by single-crystal X-ray diffraction. The latter consist of trans-cofacial π-dimers strongly ion-paired with triflate anions. Variable temperature magnetic susceptibility measurements on both the neutral and radical ion dimers indicate that they are diamagnetic over the temperature range 2–300 K.
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Julkaisija
American Chemical SocietyISSN Hae Julkaisufoorumista
0020-1669Asiasanat
Julkaisu tutkimustietojärjestelmässä
https://converis.jyu.fi/converis/portal/detail/Publication/28665896
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Rahoittaja(t)
Euroopan komissio; Suomen AkatemiaRahoitusohjelmat(t)
MSCA Marie Skłodowska-Curie Actions, H2020; Akatemiahanke, SA
The content of the publication reflects only the author’s view. The funder is not responsible for any use that may be made of the information it contains.
Lisätietoja rahoituksesta
This work was supported by the Natural Sciences and Engineering Research Council of Canada (NSERCC), the University of Jyväskylä, the Academy of Finland (projects 253907 and 289172), the European Union’s H2020 research and innovations programme (under the Marie Skłodowska-Curie Grant Agreement 659123), CNRS, the University of Bordeaux, the Région Nouvelle Aquitaine, the GdR MCM-2, and the MOLSPIN COST action CA15128. We thank the Diamond Light Source for access to beamlines I11 and I19. ...Lisenssi
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