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Non-Innocent Base Properties of 3- and 4-Pyridyl-dithia- and Diselenadiazolyl Radicals: The Effect of N-Methylation.
Taponen, Anni I; Wong, Joanne W L; Lekin, Kristina; Assoud, Abdeljalil; Robertson, Craig M; Lahtinen, Manu; Clérac, Rodolphe; Tuononen, Heikki M; Mailman, Aaron; Oakley, Richard T.
Afiliação
  • Taponen AI; Department of Chemistry , University of Jyväskylä , P.O. Box 35, Jyväskylä , Finland.
  • Wong JWL; Department of Chemistry , University of Waterloo , Waterloo , Ontario N2L 3G1 , Canada.
  • Lekin K; Department of Chemistry , University of Waterloo , Waterloo , Ontario N2L 3G1 , Canada.
  • Assoud A; Department of Chemistry , University of Waterloo , Waterloo , Ontario N2L 3G1 , Canada.
  • Robertson CM; Department of Chemistry , University of Liverpool , Liverpool , L69 7ZD , United Kingdom.
  • Lahtinen M; Department of Chemistry , University of Jyväskylä , P.O. Box 35, Jyväskylä , Finland.
  • Clérac R; Centre National de la Recherche Scientifique , CNRS, CRPP, UMR 5031, 33600 Pessac , France.
  • Tuononen HM; Université de Bordeaux , CRPP, UPR 5031, 33600 Pessac , France.
  • Mailman A; Department of Chemistry , University of Jyväskylä , P.O. Box 35, Jyväskylä , Finland.
  • Oakley RT; Department of Chemistry , University of Jyväskylä , P.O. Box 35, Jyväskylä , Finland.
Inorg Chem ; 57(21): 13901-13911, 2018 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-30351085
ABSTRACT
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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Texto completo: Disponível Coleções: Bases de dados internacionais Base de dados: MEDLINE Idioma: Inglês Revista: Inorg Chem Ano de publicação: 2018 Tipo de documento: Artigo País de afiliação: Finlândia