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Synthesis and structure of organoantimony (V) cyclometallates: transannular interactions and the barrier to cyclisation

Record type: Article

A variety of alpha-hydroxy carboxylic acid salts [AgO2CC(OH)(RR2)-R-1] react with SbPh3Cl2 1 to afford the cyclometalled complexes 4b-g. A single crystal X-ray analysis of(+/-)-4g reveals the presence of conformational diastereoisomers arising from the helical chirality of the SbPh3 propeller unit. Benzilic acid (R-1 = R-2 = Ph) however, reacts with 1 to afford the di-ester 3. To rationalise the steric impediment to cyclisation, the solid-state geometries of all known five coordinate dioxo cyclometallates possessing an integral XPh3 unit are presented, along with the accessible conformations for each structural alternative. Computer modelling and crystallographic correlations identify severe 1,3-transannular interactions within the fluxional species associated with the nascent cyclometallate of benzilic acid.

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Citation

Barucki, H., Coles, S. J., Costello, J. F. and Hursthouse, M. B. (2001) Synthesis and structure of organoantimony (V) cyclometallates: transannular interactions and the barrier to cyclisation Journal of Organometallic Chemistry, 622, (1-2), pp. 265-273. (doi:10.1016/S0022-328X(00)00923-2).

More information

Published date: 15 March 2001
Keywords: cyclometallation, antimony, 1, 3-transannular interactions penta-coordinated molecules, organometallic complexes, conformational-analysis, 5-coordinated antimony, phosphine-ligands, crystal-structure, derivatives, pentaphenylbismuth, configuration, reactivity

Identifiers

Local EPrints ID: 19396
URI: http://eprints.soton.ac.uk/id/eprint/19396
ISSN: 0022-328X
PURE UUID: a12b16a5-d2df-4330-b38e-7655fc02296a
ORCID for S. J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 13 Feb 2006
Last modified: 17 Jul 2017 16:31

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Contributors

Author: H. Barucki
Author: S. J. Coles ORCID iD
Author: J. F. Costello

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