TY - JOUR

T1 - Chlorine “Equatorial Belt” Activation of CF3Cl by CO2

T2 -  The C···Cl Tetrel Bond Dominance in CF3Cl−CO2

AU - Zheng, Yang

AU - Herbers, Sven

AU - Gou, Qian

AU - Caminati, Walther

AU - Grabow, Jens Uwe

N1 - Funding Information: We are grateful for the financial support from the National Natural Science Foundation of China (Grant No. 22073013), Fundamental Research Funds for the Central Universities (Grant No. 2020CDJXZ002), Graduate Research and Innovation Foundation of Chongqing, China (Grant No. CYB20043), and Natural Science Foundation of Chongqing, China (Grant No. cstc2018jcyjAX0050).

PY - 2021/4/29

Y1 - 2021/4/29

N2 - Besides its typical halogen donor behavior (exhibiting a Cl σ-hole) in forming Cl···B halogen bonds (B is an electron-rich region), CF3Cl reveals a new interaction site in its complex with CO2 when explored by rotational spectroscopy. Experimental evidence and theoretical analyses point out irrefutably that CF3Cl prefers to link to CO2 through its Cl "equatorial belt"consisting of the lone pairs of the Cl atom, resulting in a C···Cl tetrel bond. In addition, a secondary plausible C···O tetrel bond and a F···O halogen bond might contribute to the relative orientation of the moieties forming the complex. The effects of the Cl "equatorial belt"present in perhalogenated molecules, such as CF3Cl, have been hitherto overlooked in describing the origin of noncovalent interactions. That left a significant void that the present study tries to fill by outlining its importance.

AB - Besides its typical halogen donor behavior (exhibiting a Cl σ-hole) in forming Cl···B halogen bonds (B is an electron-rich region), CF3Cl reveals a new interaction site in its complex with CO2 when explored by rotational spectroscopy. Experimental evidence and theoretical analyses point out irrefutably that CF3Cl prefers to link to CO2 through its Cl "equatorial belt"consisting of the lone pairs of the Cl atom, resulting in a C···Cl tetrel bond. In addition, a secondary plausible C···O tetrel bond and a F···O halogen bond might contribute to the relative orientation of the moieties forming the complex. The effects of the Cl "equatorial belt"present in perhalogenated molecules, such as CF3Cl, have been hitherto overlooked in describing the origin of noncovalent interactions. That left a significant void that the present study tries to fill by outlining its importance.

UR - http://www.scopus.com/inward/record.url?scp=85105046288&partnerID=8YFLogxK

U2 - 10.1021/acs.jpclett.1c00837

DO - 10.1021/acs.jpclett.1c00837

M3 - Article

C2 - 33861087

AN - SCOPUS:85105046288

VL - 12

SP - 3907

EP - 3913

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

SN - 1948-7185

IS - 16

ER -