Premium
A Computational Study on 3‐Azonia‐, 3‐Phosphonia‐, and 3‐Arsoniaspiro[2.2]pentanes and Related Three‐Membered Heterocycles
Author(s) -
Trujillo Cristina,
SánchezSanz Goar,
Alkorta Ibon,
Elguero José
Publication year - 2014
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201402442
Subject(s) - isodesmic reaction , chemistry , cyclopropane , pentane , ring (chemistry) , computational chemistry , aromaticity , ring strain , molecule , ab initio , crystallography , ab initio quantum chemistry methods , density functional theory , stereochemistry , organic chemistry
A theoretical study at the ab initio MP2/6‐311++G(d,p) level of theory is carried out to characterize several heterocyclic spiro[2.2]pentane cations with N, P, and As as spiro atoms. The strain and relative stability of the spiropentanes are obtained through isodesmic reactions. Nucleus‐independent chemical shifts (NICS) and 3D NICS isosurfaces show σ‐aromatic characteristics, similar to those found in cyclopropane. The interaction with the Cl − anion, which results in four different stationary structures, is studied and characterized by means of the atoms in molecules methodology, and Cl ⋅⋅⋅ pnicogen, Cl ⋅⋅⋅ H, and Cl ⋅⋅⋅ C interactions are found. The most stable structure in all cases corresponds to opening of one of the three‐membered rings, due to the attack of the Cl atom, and CCl bond formation. Furthermore, the reaction with the 3‐boranuidaspiro[2.2]pentane anion results in the formation of a new compound through cleavage of one ring of both reactants.