Synthesis and structure of organoantimony (V) cyclometallates: transannular interactions and the barrier to cyclisation
Synthesis and structure of organoantimony (V) cyclometallates: transannular interactions and the barrier to cyclisation
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.
cyclometallation, antimony, 1, 3-transannular interactions
penta-coordinated molecules, organometallic complexes, conformational-analysis, 5-coordinated antimony, phosphine-ligands, crystal-structure, derivatives, pentaphenylbismuth, configuration, reactivity
265-273
Barucki, H.
598cf084-21fb-421e-8226-f109470f8f45
Coles, S. J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Costello, J. F.
53748fbc-3a08-4ebb-b5db-278bac65c9b1
Hursthouse, M. B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
15 March 2001
Barucki, H.
598cf084-21fb-421e-8226-f109470f8f45
Coles, S. J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Costello, J. F.
53748fbc-3a08-4ebb-b5db-278bac65c9b1
Hursthouse, M. B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
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), .
(doi:10.1016/S0022-328X(00)00923-2).
Abstract
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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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
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Date deposited: 13 Feb 2006
Last modified: 16 Mar 2024 03:05
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Author:
H. Barucki
Author:
J. F. Costello
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