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New N – heterocyclic mono – and disilavinylidene iron – complexes by density functional theory
Author(s) -
Soleimani Purlak Nahid,
Kassaee Mohamad Z.
Publication year - 2021
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.4148
Subject(s) - chemistry , natural bond orbital , isodesmic reaction , silylene , density functional theory , crystallography , ligand (biochemistry) , nucleophile , computational chemistry , stereochemistry , silicon , organic chemistry , biochemistry , receptor , catalysis
Recently, we found less nucleophilicity ( N ) for normally and abnormally disubstituted Arduengo‐type monosilylenes [R 2 N 4 Si:] ( 1 – 10 ) than their corresponding disilavinylidene ligands [R 2 N 4 SiSi:] ( 1′ – 10′ ). Considering the importance of silylene–iron complexes, here we compare and contrast thermodynamic properties of their novel [R 2 N 4 Si: → Fe(N(SiH 3 ) 2 ) 2 ] ( 1 c – 10 c ) and [R 2 N 4 SiSi: → Fe(N(SiH 3 ) 2 ) 2 ] iron complexes ( 1′ c – 10′ c ) , for R = H, Me, ethyl, i ‐propyl, and t ‐butyl, at B3LYP/6‐311++G**+ LANL2DZ level of theory. Isodesmic reactions show higher stability for disilavinylidenes 1′ c – 10′ c compared with their corresponding monosilylene 1 c – 10 c . In all species, the natural bond orbital (NBO) calculations show transfer of charge from the silylene (of the ligand) to iron(II). Multiple Fe–Si bonding character is detected in all complexes (Wiberg bond index > 1). Yet Fe–Si bond distances in 1′ c – 10′ c appear shorter than those in their corresponding 1 c – 10 c . Binding energy (Δ E bin ) of [Fe(N(SiH 3 ) 2 ) 2 ] with 1′ – 10′ appears higher in 1′ c – 10′ c than the corresponding 1 c – 10 c .