Premium
Can metal halides be electron donors in σ‐hole and π‐hole tetrel bonds? Cooperativity with an alkaline‐earth bond
Author(s) -
Liu Na,
Li Qingzhong
Publication year - 2021
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26771
Subject(s) - halide , cooperativity , crystallography , chemistry , alkaline earth metal , quadruple bond , bond energy , metal , alkali metal , halogen , carbon fibers , single bond , chemical bond , bond length , bond order , inorganic chemistry , molecule , materials science , crystal structure , organic chemistry , alkyl , biochemistry , composite number , composite material
The tetrel bond in the complexes of TH 3 F‐MX 2 (T = C‐Sn, M = Be and Mg; X = F, Cl, and Br) and F 2 CO‐MX 2 has been explored and it is also called carbon bond for T = C. The results show that the halogen atom of metal halide can engage in a σ‐hole interaction with TH 3 F and a π‐hole interaction with F 2 CO. A linear carbon‐bonded complex is formed between CH 3 F and MX 2 , while a cyclic structure is obtained in other complexes, where a tetrel bond coexists with an alkaline‐earth bond. The carbon bond between CH 3 F and MX 2 is weak with interaction energy less than 9 kJ/mol, depending on the nature of M and X atoms. The alkaline‐earth bond is stronger than the tetrel bond in the cyclic complexes and both interactions display positive cooperativity. The F 2 CO‐MX 2 complex is more stable than TH 3 F‐MX 2 , mainly due to the stronger alkaline‐earth bond in the former. The π‐hole carbon bond is also stronger than the σ‐hole carbon bond when a metal halide acts as an electron donor. Such tetrel‐bonded structures involving metal halides have been found in the Cambridge Structural Database.