Issue 14, 2000

Characterising secondary bonding interactions within triaryl organoantimony(V) and organobismuth(V) complexes

Abstract

The thermodynamically preferred conformations of the five-co-ordinate trigonal-bipyramidal complexes SbPh3Cl21 and BiPh3Cl2 2, determined via van der Waals energy calculations, have been found to be in good agreement with the corresponding correlated propeller arrangements which are observed in the solid state. However, similar calculations upon the corresponding diesters SbPh3(O2CR)2 3 and BiPh3(O2CR)2 4 [R = C(OH)Ph2 a or C6H4OH-o b] were at variance with the solid state, thereby indicating the participation of stabilising secondary bonding interactions between the metal centre and the carbonyl oxygen atom of the ester moiety. In accord with current Lewis acid–base bonding models, a strong correlation was found to exist between the pKa of the parent acid and the magnitude of the M  O[double bond, length half m-dash]C interaction. The complexes 3a,3b and 4a,4b were prepared in order to probe the effect of strong intramolecular hydrogen bonding upon the ability of ester ligands to stabilise sterically disfavoured conformations via σnb donation. Single crystal X-ray analyses of 3a,3b and 4a demonstrate that although significant attenuation of the M  O[double bond, length half m-dash]C interaction is achieved via strong intramolecular hydrogen bonding, sterically disfavoured arrangements predominate in the solid state.

Supplementary files

Article information

Article type
Paper
Submitted
24 Mar 2000
Accepted
22 May 2000
First published
30 Jun 2000

J. Chem. Soc., Dalton Trans., 2000, 2319-2325

Characterising secondary bonding interactions within triaryl organoantimony(V) and organobismuth(V) complexes

H. Barucki, S. J. Coles, J. F. Costello, T. Gelbrich and M. B. Hursthouse, J. Chem. Soc., Dalton Trans., 2000, 2319 DOI: 10.1039/B002337J

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