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[1,2,5]Selenadiazolo[3,4‐ c ][1,2,5]thiadiazole and [1,2,5]Selenadiazolo[3,4‐ c ][1,2,5]thiadiazolidyl – A Synthetic, Structural, and Theoretical Study
Author(s) -
Bagryanskaya Irina Yu.,
Gatilov Yuri V.,
Gritsan Nina P.,
Ikorskii Vladimir N.,
Irtegova Irina G.,
Lonchakov Anton V.,
Lork Enno,
Mews Ruediger,
Ovcharenko Victor I.,
Semenov Nikolay A.,
Vasilieva Nadezhda V.,
Zibarev Andrey V.
Publication year - 2007
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200700501
Subject(s) - chemistry , pyridinium , bridging ligand , pyridine , yield (engineering) , density functional theory , crystallography , salt (chemistry) , antiferromagnetism , ion , crystal structure , computational chemistry , medicinal chemistry , organic chemistry , materials science , physics , metallurgy , condensed matter physics
A new heterocyclic system, namely [1,2,5]selenadiazolo[3,4‐ c ][1,2,5]thiadiazole ( 1 ), has been prepared in 60 % yield by the 1:1 condensation of 3,4‐diamino‐1,2,5‐thiadiazole ( 4 ) with SeCl 4 in the presence of pyridine. The structures of 1 and its 1:1 complex with pyridinium chloride ( 5 ) have been elucidated by X‐ray diffraction (XRD). The reversible electrochemical reduction of 1 , as well as its chemical reduction with PhS – anion, provide the long‐lived [1,2,5]selenadiazolo[3,4‐ c ][1,2,5]thiadiazolidyl radical anion ( 2 ), which has been isolated in the form of the thermally stable salt [K(18‐crown‐6)][ 2 ] ( 3 ) in 75 % yield. The experimental structural and spectral characteristics of 1 and 2 agree fairly well with those obtained from density functional (DFT) calculations. The salt 3 has been characterized by ESR spectroscopy (in the solid state and in solution) and XRD. The radical anion 2 acts as a bridging ligand in crystalline 3 . Magnetic measurements on salt 3 reveal weak antiferromagnetic interactions ( J = –1.65 cm –1 ). The magnetic structures of 3 and its disulfur congener 11 have been analyzed in terms of dimeric exchange integrals calculated by spin‐unrestricted broken‐symmetry DFT and post‐HF methods.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)