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An Experimental and Theoretical Study of the Basicity of Tetra‐ tert ‐butyltetrahedrane
Author(s) -
Notario Rafael,
Castaño Obis,
Andrés José Luis,
Elguero José,
Maier Günther,
Hermann Christian
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20010119)7:2<342::aid-chem342>3.0.co;2-y
Subject(s) - tetra , chemistry , protonation , ab initio , computational chemistry , cyclobutadiene , gas phase , ammonia , mass spectrometry , ab initio quantum chemistry methods , ammonium , standard enthalpy of formation , ion , medicinal chemistry , organic chemistry , molecule , chromatography
The gas‐phase basicity (GB) of tetra‐ tert ‐butyltetrahedrane ( t Bu 4 THD) was determined by FT‐ICR mass spectrometry and comparison with reference compounds of known basicity. Its GB, 1035±10 kJ mol −1 , makes tetra‐ tert ‐butyltetrahedrane one of the strongest bases reported so far. Ab initio calculations [B3LYP/6‐31G(d) and B3LYP/6‐311+G(d,p)//6‐31G(d)] have been carried out in order to compare the high experimental basicity of t Bu 4 THD with that estimated theoretically. Both B3LYP/6‐31G(d) and QCISD(T) calculations were used to determine the reaction path which connects the initial tetrahedrane–ammonium complex with the final products, protonated cyclobutadiene (CBDH + ) and ammonia.