✍ Scribed by Nicholas G. White; Jonathan A. Kitchen; Sally Brooker
No coin nor oath required. For personal study only.
Eight mononuclear nickel(II) complexes of the ligands 4‐amino‐3,5‐di(2‐pyridyl)‐1,2,4‐triazole (adpt) and 4‐pyrrolyl‐3,5‐di(2‐pyridyl)‐1,2,4‐triazole (pldpt) with the anions ClO~4~, BF~4~, PF~6~ and SbF~6~ have been prepared. In all cases the metal/ligand ratio is 1:3, and the complexes are of the form NiL~3~~2~·solvents where L = adpt or pldpt and A = one of the aforementioned anions. Five of these complexes have been structurally characterized by X‐ray crystallography: four of these contain pldpt and strong anion–π interactions are observed, with two motifs present in all four structures. One of the anions occupies a “π‐pocket” formed by two coordinated triazole rings and one coordinated pyridine ring. The other anion only interacts with one triazole ring, which is involved in the pocket around the first anion, such that the triazole ring is “sandwiched” by two anions. Surprisingly, in all four of these complexes, the two triazole centroid···anion distances in the anion–triazole–anion interactions [2.917(7)–3.005(10) Å] are significantly shorter than in any of the other types of triazole–anion interactions [3.164(5)–3.456(9) Å].(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
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## Abstract Several complexes of tropylium (**1**) with anions are optimized at the RI‐MP2(full)/6‐31++G\*\* level of theory. This binding unit can interact very favorably with anions, and it combines the strength of the electrostatic interaction with the directionality of the anion–π interaction.