Enhanced acidity of cyclopenta-2,4-dienylborane and its Al and Ga analogues. The role of aromatization

Literature Information

Publication Date 2009-07-27
DOI 10.1039/B906045F
Impact Factor 3.676
Authors

Jean-Claude Guillemin


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Abstract

The intrinsic acidity of cyclopenta-2,4-dienylborane and its Al and Ga analogues has been compared to that of cyclopentadiene by means of B3LYP/6-311+G(3df,2p)//CCSD/6-311+G(d,p) calculations. Substitution of one of the H atoms of the C(sp3)H2group of cyclopentadiene by an XH2 (X = B, Al, Ga) leads to an acidity enhancement which is significantly large for the boron derivative (95 kJ mol−1); but much smaller for the Al and Ga containing analogues. This acidity enhancement reflects the stabilization of the anion, in the substituted derivatives, due to a significant reinforcement of the C–X bond. This enhancement is however smaller than expected because, although XH2 (X = B, Al, Ga) substitution leads to a significant aromatization of the neutral compounds, the aromaticity significantly decreases upon deprotonation, whereas for the unsubstituted parent compound is the other way around. Cyclopenta-2,4-dienylborane and its Al and Ga analogues behave as highly fluxional systems.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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