The University of Southampton
University of Southampton Institutional Repository

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
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
0022-328X
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
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), 265-273. (doi:10.1016/S0022-328X(00)00923-2).

Record type: Article

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.

Full text not available from this repository.

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: https://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: 06 Jun 2018 12:54

Export record

Altmetrics

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of https://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×