Document Detail

Unexpected Acidity Enhancement Triggered by AlH3 Association to Phosphines.
MedLine Citation:
PMID:  22630168     Owner:  NLM     Status:  Publisher    
The complexes formed by the interaction between a series of phosphines, R-PH2 (R = H, CH3, c-C3H5, C6H5) and AlH3 have been investigated through the use of high-level G4 ab initio calculations. These very stable complexes behave as much stronger acids than the isolated phosphines. This dramatic acidity enhancement, which can be as high as 174 kJ mol-1, results from a much greater stabilization of the anionic deprotonated species with respect to the neutral one, upon AlH3 association. This effect depends quantitatively on the nature of the substituent R, and is smaller for R=C6H5 because of the conjugation of the P lone-pair with the aromatic system. More unexpectedly however, the phosphine-alane complexes, RPH2:AlH3 are more acidic than the corresponding phosphineborane RPH2:BH3 analogues. This unexpected result is due to the enhanced stability of the anionic deprotonated species for complexes involving AlH3, because the delocalization of the newly created P lone-pair with the P-Al bonding density is more favorable when the Lewis acid is aluminum trihydride than when it is borane.
Ana Martín-Sómer; Al Mokhtar Lamsabhi; Otilia Mo; Manuel Yáñez
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-5-25
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  -     ISSN:  1520-5215     ISO Abbreviation:  -     Publication Date:  2012 May 
Date Detail:
Created Date:  2012-5-28     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
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