ISSN:
0947-6539
Keywords:
ab initio calculations
;
gold
;
isolobal relationship
;
sulfonium trication
;
superelectrophiles
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The pentahydridosulfonium trication SH3+5 was found by ab initio MP2/ 6-31G** and QCISD(T)/6-311G** levels of calculation to be a stable minimum with Cs symmetric structure 1. It is isostructural with the parent pentacoordinate carbonium ion CH+5. Structure 1 resembles a complex between SH3+3 and molecular hydrogen forming a 2e-3c bond. This structure involving a pentaco-ordinate sulfur atom is unprecedented. Rotation of the H2 unit around the pseudo-C3 axis of SH3 is facile. The structure of SF3+5 was also calculated and compared with that of 1. In addition, our studies at the ab initio MP2/6-31G** level showed that the parent pentacoordinate oxonium trication OH3+5 is not a minimum on its potential energy surface, and dissociation into OH2+4 and H+ occurs upon optimization.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19970030709
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