1,2,4,5-Tetrazine: an unprecedented mu4-coordination that enhances ability for anion···pi interactions

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dc.contributor.author Gural'skiy, Il'ya A.
dc.contributor.author Escudero, Daniel
dc.contributor.author Frontera Beccaria, Antonio
dc.contributor.author Solntsev, Paulo V.
dc.contributor.author Rusanov, Eduard B.
dc.contributor.author Chernega, Alexander N.
dc.contributor.author Krautscheid, Harald
dc.contributor.author Domasevitch, Konstantin V.
dc.date.accessioned 2018-11-15T10:53:06Z
dc.identifier.uri http://hdl.handle.net/11201/148523
dc.description.abstract [eng] A series of framework coordination polymers reveals the use of 1,2,4,5-tetrazines as efficient bridging ligands towards silver(I) and copper(I) ions. All four nitrogen atoms were functional as lone pair donors leading to an unprecedented m4-coordination of the ligands (1,2,4,5-tetrazine, ttz; 3,6-dimethyl-1,2,4,5-tetrazine, Me2ttz) in [Ag(ttz)(X)] (X = NO3, 1; ClO4, 2), [Ag2(Me2ttz)(NO3)2] (3), [Ag2(Me2ttz)(H2O)2(ClO4)2] (4), [Ag3(Me2ttz)(H2O)2(CF3SO3)3] (5) and [Cu4Cl4(Me2ttz)] (6). In 1 and 2, m4-tetrazines and silver ions (AgN4, Ag-N 2.42-2.53A˚ ) compose a 3D framework of {42;84} topology. Structures 3 and 4 were based on disilver-tetrazine ribbons, while in 5 m4-tetrazines interconnect silver-triflate chains. In 6, m4-ligands connect inorganic layers sustained by copper-chloride squares, hexa- and octagons (1.974(2) and 1.981(2)A˚ ). Multiple N-coordination to metal ions enhances the ability of the electron deficient tetrazine system for anion ◊ ◊ ◊ p binding. Compounds 1 and 2 exhibit very short interactions of this type with corresponding O◊ ◊ ◊ C(N) separations down to a record value of 2.78A˚ and O◊ ◊ ◊ p 2.61A˚ . For 6, p-acidity of tetrazine was reflected by contacts Cl ◊ ◊ ◊ p of 3.30A˚ . Results of high level ab initio calculations (RI-MP2/aug-cc-pVTZ) were in good agreement with experimental results, and were suggestive of the progressive enhancement of the p-acidity by increasing the number of Ag(I) ions N-coordinated to tetrazine.
dc.format application/pdf
dc.relation.isformatof Versió postprint del document publicat a: https://doi.org/10.1039/B818125J
dc.relation.ispartof Dalton Transactions, 2009, num. 15, p. 2856-2864
dc.rights (c) Gural'skiy, Il'ya A. et al., 2009
dc.subject.classification 54 - Química
dc.subject.other 54 - Chemistry. Crystallography. Mineralogy
dc.title 1,2,4,5-Tetrazine: an unprecedented mu4-coordination that enhances ability for anion···pi interactions
dc.type info:eu-repo/semantics/article
dc.type info:eu-repo/semantics/acceptedVersion
dc.date.updated 2018-11-15T10:53:07Z
dc.date.embargoEndDate info:eu-repo/date/embargoEnd/2075-01-01
dc.embargo 2075-01-01
dc.rights.accessRights info:eu-repo/semantics/embargoedAccess
dc.identifier.doi https://doi.org/10.1039/B818125J

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