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Theoretical study on the isomeric structures and the stability of silylenoid (Tsi)Cl 2 SiLi (Tsi = C(SiMe 3 ) 3 )
Author(s) -
Xie Ju,
Feng Dacheng,
Feng Shengyu
Publication year - 2006
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20395
Subject(s) - stability (learning theory) , computational chemistry , thermodynamics , chemistry , materials science , physics , computer science , machine learning
The structures and isomerization of silylenoid (Tsi)Cl 2 SiLi (Tsi = C(SiMe 3 ) 3 ) were studied by density functional theory (DFT) at the B3LYP/6‐31G(d) level. Four equilibrium structures and three isomeric transition states were located. The three‐membered ring and p ‐complex structures, 1 and 2, are the two most stable forms. Two other local minima, the σ‐complex 3 and tetrahedron structure 4, should rearrange to 1 with very low barriers, and then to the most stable isomer 2. To exploit further the stability of silylenoid (Tsi)Cl 2 SiLi, the insertion reactions of 2 and silylene (Tsi)ClSi into the HF molecule have been investigated at the B3LYP/6‐31G(d) level, respectively. The results show that the insertion of 2 into HF is very similar to that of (Tsi)ClSi into HF, but the latter is more favorable. To probe the influence of the substituent Tsi on the stability of silylenoid (Tsi)Cl 2 SiLi, the isomers and insertion reaction of silylenoid CH 3 Cl 2 SiLi were investigated in a similar way of those with (Tsi)Cl 2 SiLi. The results indicate that silylenoid containing very bulky group Tsi exhibits unusual stability because of the severe steric hindrance produced by Tsi at the center to which it is attached. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 933–940, 2006