Counterion influence on the N-I-N halogen bond

J 2015

Counterion influence on the N-I-N halogen bond

BEDIN, Michele, Alavi KARIM, Marcus REITTI, Anna-Carin C. CARLSSON, Filip TOPIC et. al.

Basic information

Original name

Counterion influence on the N-I-N halogen bond

Authors

BEDIN, Michele (752 Sweden), Alavi KARIM (752 Sweden), Marcus REITTI (752 Sweden), Anna-Carin C. CARLSSON (752 Sweden), Filip TOPIC (246 Finland), Mario CETINA (191 Croatia), Fangfang PAN (246 Finland), Václav HAVEL (203 Czech Republic, belonging to the institution), Fatima AL-AMERI (752 Sweden), Vladimír ŠINDELÁŘ (203 Czech Republic, belonging to the institution), Kari RISSANEN (246 Finland), Jurgen GRAFENSTEIN (752 Sweden) and Mate ERDELYI (752 Sweden, guarantor)

Edition

CHEMICAL SCIENCE, CAMBRIDGE (ENGLAND), ROYAL SOC CHEMISTRY, 2015, 2041-6520

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10401 Organic chemistry

Country of publisher

United Kingdom of Great Britain and Northern Ireland

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 9.144

RIV identification code

RIV/00216224:14310/15:00081646

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1039/c5sc01053e

UT WoS

000356176200011

Keywords in English

EFFECTIVE CORE POTENTIALS; MOLECULAR-ORBITAL METHODS; HYDROGEN-BONDS; IODONIUM NITRATE; BASIS-SET; ELECTROPHILIC ADDITIONS; PENTENYL GLYCOSIDES; RESONANCE-SPECTRA; NMR-SPECTROSCOPY;

Abstract

V originále

A detailed investigation of the influence of counterions on the [N-I-N](+) halogen bond in solution, in the solid state and in silico is presented. Translational diffusion coefficients indicate close attachment of counterions to the cationic, three-center halogen bond in dichloromethane solution. Isotopic perturbation of equilibrium NMR studies performed on isotopologue mixtures of regioselectively deuterated and nondeuterated analogues of the model system showed that the counterion is incapable of altering the symmetry of the [N-I-N](+) halogen bond. This symmetry remains even in the presence of an unfavorable geometric restraint. A high preference for the symmetric geometry was found also in the solid state by single crystal X-ray crystallography. Molecular systems encompassing weakly coordinating counterions behave similarly to the corresponding silver(I) centered coordination complexes. In contrast, systems possessing moderately or strongly coordinating anions show a distinctly different behavior. Such silver(I) complexes are converted into multi-coordinate geometries with strong Ag-O bonds, whereas the iodine centered systems remain linear and lack direct charge transfer interaction with the counterion, as verified by N-15 NMR and DFT computation. This suggests that the [N-I-N](+) halogen bond may not be satisfactorily described in terms of a pure coordination bond typical of transition metal complexes, but as a secondary bond with a substantial charge-transfer character.

Links

GA13-15576S, research and development project

Name: Syntéza a supramolekulární vlastnosti bambusurilů

Investor: Czech Science Foundation

Citovat

BEDIN, Michele, Alavi KARIM, Marcus REITTI, Anna-Carin C. CARLSSON, Filip TOPIC, Mario CETINA, Fangfang PAN, Václav HAVEL, Fatima AL-AMERI, Vladimír ŠINDELÁŘ, Kari RISSANEN, Jurgen GRAFENSTEIN and Mate ERDELYI. Counterion influence on the N-I-N halogen bond. CHEMICAL SCIENCE. CAMBRIDGE (ENGLAND): ROYAL SOC CHEMISTRY, 2015, vol. 6, No 7, p. 3746-3756. ISSN 2041-6520. Available from: https://dx.doi.org/10.1039/c5sc01053e.

@article{1339490,
   author = {Bedin, Michele and Karim, Alavi and Reitti, Marcus and Carlsson, AnnaandCarin C. and Topic, Filip and Cetina, Mario and Pan, Fangfang and Havel, Václav and AlandAmeri, Fatima and Šindelář, Vladimír and Rissanen, Kari and Grafenstein, Jurgen and Erdelyi, Mate},
   article_location = {CAMBRIDGE (ENGLAND)},
   article_number = {7},
   doi = {http://dx.doi.org/10.1039/c5sc01053e},
   keywords = {EFFECTIVE CORE POTENTIALS; MOLECULAR-ORBITAL METHODS; HYDROGEN-BONDS; IODONIUM NITRATE; BASIS-SET; ELECTROPHILIC ADDITIONS; PENTENYL GLYCOSIDES; RESONANCE-SPECTRA; NMR-SPECTROSCOPY;},
   language = {eng},
   issn = {2041-6520},
   journal = {CHEMICAL SCIENCE},
   title = {Counterion influence on the N-I-N halogen bond},
   url = {http://pubs.rsc.org/en/Content/ArticleLanding/2015/SC/C5SC01053E#!divAbstract},
   volume = {6},
   year = {2015}
}

TY  - JOUR
ID  - 1339490
AU  - Bedin, Michele - Karim, Alavi - Reitti, Marcus - Carlsson, Anna-Carin C. - Topic, Filip - Cetina, Mario - Pan, Fangfang - Havel, Václav - Al-Ameri, Fatima - Šindelář, Vladimír - Rissanen, Kari - Grafenstein, Jurgen - Erdelyi, Mate
PY  - 2015
TI  - Counterion influence on the N-I-N halogen bond
JF  - CHEMICAL SCIENCE
VL  - 6
IS  - 7
SP  - 3746-3756
EP  - 3746-3756
PB  - ROYAL SOC CHEMISTRY
SN  - 20416520
KW  - EFFECTIVE CORE POTENTIALS
KW  - MOLECULAR-ORBITAL METHODS
KW  - HYDROGEN-BONDS
KW  - IODONIUM NITRATE
KW  - BASIS-SET
KW  - ELECTROPHILIC ADDITIONS
KW  - PENTENYL GLYCOSIDES
KW  - RESONANCE-SPECTRA
KW  - NMR-SPECTROSCOPY;
UR  - http://pubs.rsc.org/en/Content/ArticleLanding/2015/SC/C5SC01053E#!divAbstract
L2  - http://pubs.rsc.org/en/Content/ArticleLanding/2015/SC/C5SC01053E#!divAbstract
N2  - A detailed investigation of the influence of counterions on the [N-I-N](+) halogen bond in solution, in the solid state and in silico is presented. Translational diffusion coefficients indicate close attachment of counterions to the cationic, three-center halogen bond in dichloromethane solution. Isotopic perturbation of equilibrium NMR studies performed on isotopologue mixtures of regioselectively deuterated and nondeuterated analogues of the model system showed that the counterion is incapable of altering the symmetry of the [N-I-N](+) halogen bond. This symmetry remains even in the presence of an unfavorable geometric restraint. A high preference for the symmetric geometry was found also in the solid state by single crystal X-ray crystallography. Molecular systems encompassing weakly coordinating counterions behave similarly to the corresponding silver(I) centered coordination complexes. In contrast, systems possessing moderately or strongly coordinating anions show a distinctly different behavior. Such silver(I) complexes are converted into multi-coordinate geometries with strong Ag-O bonds, whereas the iodine centered systems remain linear and lack direct charge transfer interaction with the counterion, as verified by N-15 NMR and DFT computation. This suggests that the [N-I-N](+) halogen bond may not be satisfactorily described in terms of a pure coordination bond typical of transition metal complexes, but as a secondary bond with a substantial charge-transfer character.
ER  -

BEDIN, Michele, Alavi KARIM, Marcus REITTI, Anna-Carin C. CARLSSON, Filip TOPIC, Mario CETINA, Fangfang PAN, Václav HAVEL, Fatima AL-AMERI, Vladimír ŠINDELÁŘ, Kari RISSANEN, Jurgen GRAFENSTEIN and Mate ERDELYI. Counterion influence on the N-I-N halogen bond. \textit{CHEMICAL SCIENCE}. CAMBRIDGE (ENGLAND): ROYAL SOC CHEMISTRY, 2015, vol.~6, No~7, p.~3746-3756. ISSN~2041-6520. Available from: https://dx.doi.org/10.1039/c5sc01053e.

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