An experimental and theoretical study of the basicity of tetra-tert-butyltetrahedrane.
The gas-phase basicity (GB) of tetra-tert-butyltetrahedrane (tBu4THD) was determined by FT-ICR mass spectrometry and comparison with reference compounds of known basicity. Its GB, 1035+/-10 kJ x 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 tBu4THD 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.
Instituto de Química Física Rocasolano, CSIC Serrano, Madrid, Spain.
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Notario
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Castaño
J L
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Andrés
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Elguero
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Maier
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Hermann