Non-Innocent Base Properties of 3- and 4‑Pyridyl-dithia- and Diselenadiazolyl Radicals: The Effect of <i>N</i>‑Methylation

Published on 2018-10-11T14:07:42Z (GMT) by
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 η<sup>2</sup>-S<sub>2</sub>---N­(py) intermolecular secondary bonding interactions. Methylation of the persilylated (iso)­nicotinimide-amides prior to condensation with sulfur monochloride leads to <i>N</i>-methylated double chloride salts Me­[3-, 4-pyDTDA]­[Cl]<sub>2</sub>, which can be converted by metathesis into the corresponding triflates Me­[3-, 4-pyDTDA]­[OTf]<sub>2</sub> and then reduced to the <i>N</i>-methylated radical triflates Me­[3-, 4-pyDTDA]­[OTf]. The crystal structures of both the <i>N</i>-methylated double triflate and radical triflate salts have been determined by single-crystal X-ray diffraction. The latter consist of <i>trans</i>-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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Taponen, Anni I.; W. L. Wong, Joanne; Lekin, Kristina; Assoud, Abdeljalil; Robertson, Craig M.; Lahtinen, Manu; et al. (2018): Non-Innocent Base Properties of 3- and 4‑Pyridyl-dithia-

and Diselenadiazolyl Radicals: The Effect of N‑Methylation. ACS Publications. Collection.