Strong dissimilarities between the gas-phase acidities of saturated and alpha,beta-unsaturated boranes and the corresponding alanes and gallanes.
The effect that unsaturation has on the intrinsic acidity of boranes, alanes, and gallanes, was analyzed by B3 LYP and CCSD(T)/6-311+G(3df,2p) calculations on methyl-, ethyl-, vinyl-, and ethynylboranes, -alanes and -gallanes, and on the corresponding hydrides XH3. Quite unexpectedly, methylborane, which behaves as a carbon acid, is predicted to have an intrinsic acidity almost 200 kJ mol(-1) stronger than BH3, reflecting the large reinforcement of the C--B bond, which upon deprotonation becomes a double bond through the donation of the lone pair created on the carbon atom into the empty p orbital of the boron. Also unexpectedly, and for the same reason, the saturated and alpha,beta-unsaturated boranes are much stronger acids than the corresponding hydrocarbons, in spite of being carbon acids as well. The Al derivatives also behave as carbon acids, but in this case the most favorable deprotonation process occurs at C beta, leading to the formation of rather stable three-membered rings, again through the donation of the C beta lone pair into the empty p orbital of Al. For Ga-containing compounds the deprotonation of the GaH2 group is the most favorable process. Therefore only Ga derivatives behave similarly to the analogues of Groups 14, 15, and 16 of the periodic table, and the saturated derivatives exhibit a weaker acidity than the unsaturated ones. Within Group 13, boranes are stronger acids than alanes and gallanes. For ethyl and vinyl derivatives, alanes are stronger acids than gallanes. We have shown, for the first time, that acidity enhancement for primary heterocompounds is not only dictated by the position of the heteroatom in the periodic table and the nature of the substituent, but also by the bonding rearrangements triggered by the deprotonation of the neutral acid.
Gámez
José A
JA
Departamento de Química, C-9, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid, Spain.
Guillemin
Jean-Claude
JC
Mó
Otilia
O
Yáñez
Manuel
M
D000535:Aluminum / Q000737:chemistry*; D001880:Boranes / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D005708:Gallium / Q000737:chemistry*; D005740:Gases / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D008956:Models, Chemical; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*
D001880:Boranes; D005609:Free Radicals; D005740:Gases; D009942:Organometallic Compounds; D005708:Gallium; D000535:Aluminum