Issue 15, 2009
From the journal:

Dalton Transactions

1,2,4,5-Tetrazine: an unprecedented μ4-coordination that enhances ability for anion⋯π interactions†

Il'ya A. Gural'skiy,a   Daniel Escudero,b   Antonio Frontera,*b   Pavlo V. Solntsev,a   Eduard B. Rusanov,c   Alexander N. Chernega,c   Harald Krautscheidd  and  Konstantin V. Domasevitch*a  

* Corresponding authors

a Inorganic Chemistry Dpt, Kiev University, Volodimirska Str. 64, Kiev, Ukraine
E-mail: dk@univ.kiev.ua

b Departament de Quimica, Universitat de les Illes Balears, Palma de Mallorca, Spain

c Institute of Organic Chemistry, Murmanskaya Str. 4, Kiev, Ukraine

d Institut für Anorganische Chemie, Universität Leipzig, Johannisallee 29, Leipzig, Deutschland

Abstract

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 μ4-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, μ4-tetrazines and silver ions (AgN4, Ag–N 2.42–2.53 Å) compose a 3D framework of {42;84} topology. Structures 3 and 4 were based on disilver–tetrazine ribbons, while in 5μ4-tetrazines interconnect silver–triflate chains. In 6, μ4-ligands connect inorganic layers sustained by copper–chloride squares, hexa- and octagons (1.974(2) and 1.981(2) Å). Multiple N-coordination to metal ions enhances the ability of the electron deficient tetrazine system for anion⋯π binding. Compounds 1 and 2 exhibit very short interactions of this type with corresponding O⋯C(N) separations down to a record value of 2.78 Å and O⋯π 2.61 Å. For 6, π-acidity of tetrazine was reflected by contacts Cl⋯π of 3.30 Å. 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 π-acidity by increasing the number of Ag(I) ions N-coordinated to tetrazine.

Graphical abstract: 1,2,4,5-Tetrazine: an unprecedented μ4-coordination that enhances ability for anion⋯π interactions

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Article information

DOI
https://doi.org/10.1039/B818125J
Article type
Paper
Submitted
15 Oct 2008
Accepted
06 Feb 2009
First published
24 Feb 2009

Dalton Trans., 2009, 2856-2864

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1,2,4,5-Tetrazine: an unprecedented μ4-coordination that enhances ability for anion⋯π interactions

I. A. Gural'skiy, D. Escudero, A. Frontera, P. V. Solntsev, E. B. Rusanov, A. N. Chernega, H. Krautscheid and K. V. Domasevitch, Dalton Trans., 2009, 2856 DOI: 10.1039/B818125J

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