Reactions of Halogens/Interhalogens with Polypyridyl Substrates: The Case of 2,4,6‐Tris(2‐pyridyl)‐1,3,5‐triazine

Abstract

The reactions between 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine (tptz) and halogens (Br2, I2) or interhalogens (ICl, IBr) yielded different products isolated in the solid state. (Htptz+)(Br3–), (Htptz+)(IBr2–), (H3tptz3+)(I3Br4–)(IBr2–)2, and (H3tptz3+)(ICl2–)3, obtained from the reactions between tptz and Br2, IBr, and ICl, were characterized by single‐crystal X‐ray diffraction and FT‐Raman spectroscopy. All compounds are salts containing the protonated donor counterbalanced by polyhalide anions of various complexity. In particular, in (H3tptz3+)(I3Br4–)(IBr2–)2 the first example of a planar I3Br4– moiety can be observed. In the case of the reaction between tptz and I2, the elemental analysis of the product indicates a 1:1 molar ratio between tptz and I2, but the FT‐Raman spectrum is not consistent with the formation of a simple adduct, clearly indicating the simultaneous presence of diiodine and symmetric triiodide. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

From Square‐Planar [ICl4]− to Novel Chloroiodates(III)? A Systematic Experimental and Theoretical Investigation of Their Ionic Liquids

“…[7] By combining more than one kind of halogen, for example dihalogens X 2 or interhalogens XY n with halidesZ À ,agreat variety of polyinterhalogenm onoanions is accessible. [2] The structure of the penta-andhepta-interhalogen monoanions with am aximum oxidation state of Ii ss imilart ot heir homoatomic counterparts, thoughf or example in the case of [I 3 Br 4 ] À ,b oth at rigonal planar [20] and at rigonal pyramidal [19] conformation was found. After ar earrangement reaction, the formal oxidation state of ÀIw ill reside on the more electronegative elements Xo rY .I f restricting the possible combinations by allowing only two elements, still two general building principles exist.…”

Multimetallic compounds containing cyclometalated Ir(III) units: Synthesis, structure, electrochemistry and photophysical properties

“…A rich chemistry of transition metal-tptz compounds has developed in recent years including their applications in supramolecular chemistry, electrochemistry and photophysics [42][43][44][45]. However, hydrolysis of tptz to bis-(2-pyridylcarbonyl)amide anion has been reported in the presence of Rh III in aqueous-alcohol solution [46,47].…”

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine

“…Eight years later, in 2008, Aragoni et al. synthesized a planar [I 3 Br 4 ] − anion in [H 3 tptz][I 3 Br 4 ][IBr 2 ] 2 (tptz=2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine) . An interlaced structure of two [I 3 Br 4 ] − anions was obtained in [CoCp 2 ] 2 [I 3 Br 4 ] 2 ⋅CH 2 Cl 2 (Figure )…”