A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Substituent Effects on the [N−I−N]+ Halogen Bond (2016)
Carlsson, A.-C. C., Mehmeti, K., Uhrbom, M., Karim, A., Bedin, M., Puttreddy, R., Kleinmaier, R., Neverov, A. A., Nekoueishahraki, B., Gräfenstein, J., Rissanen, K., & Erdélyi, M. (2016). Substituent Effects on the [N−I−N]+ Halogen Bond. Journal of the American Chemical Society, 138(31), 9853-9863. https://doi.org/10.1021/jacs.6b03842
JYU-tekijät tai -toimittajat
Julkaisun tiedot
Julkaisun kaikki tekijät tai toimittajat: Carlsson, Anna-Carin C.; Mehmeti, Krenare; Uhrbom, Martin; Karim, Alavi; Bedin, Michele; Puttreddy, Rakesh; Kleinmaier, Roland; Neverov, Alexei A.; Nekoueishahraki, Bijan; Gräfenstein, Jürgen; et al.
Lehti tai sarja: Journal of the American Chemical Society
ISSN: 0002-7863
eISSN: 1520-5126
Julkaisuvuosi: 2016
Volyymi: 138
Lehden numero: 31
Artikkelin sivunumerot: 9853-9863
Kustantaja: American Chemical Society
Julkaisumaa: Yhdysvallat (USA)
Julkaisun kieli: englanti
DOI: https://doi.org/10.1021/jacs.6b03842
Julkaisun avoin saatavuus: Avoimesti saatavilla
Julkaisukanavan avoin saatavuus: Osittain avoin julkaisukanava
Julkaisu on rinnakkaistallennettu (JYX): https://jyx.jyu.fi/handle/123456789/51083
Tiivistelmä
We have investigated the influence of electron density on the three-center [N–I–N]+ halogen bond. A series of [bis(pyridine)iodine]+ and [1,2-bis((pyridine-2-ylethynyl)benzene)iodine]+ 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 15N NMR and by computation of the natural atomic population and the π electron population of the nitrogen atoms. Formation of the [N–I–N]+ halogen bond resulted in >100 ppm 15N NMR coordination shifts. Substituent effects on the 15N NMR chemical shift are governed by the π 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···I···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.
YSO-asiasanat: molekyylit; kemialliset sidokset; supramolekulaarinen kemia
Vapaat asiasanat: halogeenisidos
Liittyvät organisaatiot
Hankkeet, joissa julkaisu on tehty
- Heikot vuorovaikutukset itsejärjestäytyvien molekyylisysteemien rakenneosina
- Rissanen, Kari
- Suomen Akatemia
OKM-raportointi: Kyllä
Raportointivuosi: 2016
JUFO-taso: 3