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Substituent Effects on the [N-I-N](+) Halogen Bond
Univ Gothenburg, Dept Chem & Mol Biol, SE-41296 Gothenburg, Sweden.;Colorado State Univ, Dept Biochem & Mol Biol, Ft Collins, CO 80523 USA..
Univ Gothenburg, Dept Chem & Mol Biol, SE-41296 Gothenburg, Sweden..
Univ Gothenburg, Dept Chem & Mol Biol, SE-41296 Gothenburg, Sweden.;AstraZeneca, CVMD iMED, Pepparedsleden 1, S-43183 Molndal, Sweden..
Univ Gothenburg, Dept Chem & Mol Biol, SE-41296 Gothenburg, Sweden..
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2016 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 138, no 31, 9853-9863 p.Article in journal (Refereed) Published
Abstract [en]

We have investigated the influence of electron density on the three-center [N-I-N](+) halogen bond. A series of [bis(pyri din e) io dine](+) and [1,2-bis ( (pyridin e-2-71 ethynyl)b e nze n e)io dine](+) BF4- complexes substituted with electron withdrawing and donating functionalities in the para-position of their pyridine nitrogen were synthesized and studied by spectroscopic and computational methods. The systematic change of electron density of the pyridine nitrogens upon alteration of the para-substituent (NO2, CF3, H, F, Me, OMe, NMe2) was confirmed by N-15 NMR and by computation of the natural atomic population and the pi electron population of the nitrogen atoms. Formation of the [N-I-N](+) halogen bond resulted in >100 ppm N-15 NMR coordination shifts. Substituent effects on the N-15 NMR chemical shift are governed by the pi population rather than the total electron population at the nitrogens. Isotopic perturbation of equilibrium NMR studies along with computation on the DFT level indicate that all studied systems possess static, symmetric [N-I-N](+) halogen bonds, independent of their electron density. This was further confirmed by single crystal X-ray diffraction data of 4-substituted [bis(pyridine)iodine](+) complexes. An increased electron density of the halogen bond acceptor stabilizes the [N center dot center dot center dot I center dot center dot center dot N](+) bond, whereas electron deficiency reduces the stability of the complexes, as demonstrated by UV-kinetics and computation. In contrast, the N-I bond length is virtually unaffected by changes of the electron density. The understanding of electronic effects on the [N-X-N](+) halogen bond is expected to provide a useful handle for the modulation of the reactivity of [bis(pyridine)halogen](+)-type synthetic reagents.

Place, publisher, year, edition, pages
2016. Vol. 138, no 31, 9853-9863 p.
National Category
Chemical Sciences
URN: urn:nbn:se:uu:diva-303055DOI: 10.1021/jacs.6b03842ISI: 000381332300021PubMedID: 27265247OAI: oai:DiVA.org:uu-303055DiVA: diva2:970693
EU, European Research Council, 259638Swedish Research Council, 2007:4407; 621-2008-3562
Available from: 2016-09-14 Created: 2016-09-14 Last updated: 2016-09-14Bibliographically approved

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