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Preparation and properties of sterically demanding and chiral distibine ligands

Preparation and properties of sterically demanding and chiral distibine ligands
Preparation and properties of sterically demanding and chiral distibine ligands
A series of new rigid distibines, 1,8-bis(R2Sb)naphthalene (R = Me: ( 1); R = Ph: ( 2)), and chiral distibines, 2,2-bis(R2Sb)-1,1-binaphthyl (R = Me: ( 3); R = Ph: ( 4) obtained as racemic mixtures) and the discrete enantiomers of 4,5-bis((R2Sb)methyl)-2,2-dimethyl-1,3-D/L-dioxolane (R = Me: ( 5) (L), ( 7) (D); R = Ph: ( 6) (L), ( 8) (D)) have been obtained in high yields, using either electrophilic halostibine reagents with di-lithium reagents (( 1)–( 4)) or nucleophilic stibide reagents with dibromo-derivatives (( 5)–( 8)).

The distorted octahedral complexes [Mo(CO)4(L)], L = ( 1)–( 8), planar [PtCl2(L)], L = ( 1), ( 2), ( 3), ( 5), and neutral, five-coordinate [RhCl(cod)(L)], L = ( 2), ( 4), ( 6), are reported and trends in the spectroscopic data are discussed in terms of the ligand donor properties. Crystal structures of ( 3) and [Mo(CO)4( 3)] reveal significant structural changes occur upon coordination, and these are also reflected in the solution NMR spectroscopic parameters.

Changes in the C–Sb–C angles and C–Sb bond distances upon coordination of ( 3) are discussed in term of increased s/p orbital mixing. Air oxidation of ( 1) forms a very unusual stibine oxide, the structure of which shows a distorted Sb4O4 cubane core (bridging O atoms) with two orthogonal naphthalene units.
0300-9246
5774-5782
Jura, Marek
e4a8ae2b-5609-45bb-99d8-a2320b9c89b9
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Jura, Marek
e4a8ae2b-5609-45bb-99d8-a2320b9c89b9
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

Jura, Marek, Levason, William, Reid, Gillian and Webster, Michael (2008) Preparation and properties of sterically demanding and chiral distibine ligands. Dalton Transactions, (42), 5774-5782. (doi:10.1039/b808493a).

Record type: Article

Abstract

A series of new rigid distibines, 1,8-bis(R2Sb)naphthalene (R = Me: ( 1); R = Ph: ( 2)), and chiral distibines, 2,2-bis(R2Sb)-1,1-binaphthyl (R = Me: ( 3); R = Ph: ( 4) obtained as racemic mixtures) and the discrete enantiomers of 4,5-bis((R2Sb)methyl)-2,2-dimethyl-1,3-D/L-dioxolane (R = Me: ( 5) (L), ( 7) (D); R = Ph: ( 6) (L), ( 8) (D)) have been obtained in high yields, using either electrophilic halostibine reagents with di-lithium reagents (( 1)–( 4)) or nucleophilic stibide reagents with dibromo-derivatives (( 5)–( 8)).

The distorted octahedral complexes [Mo(CO)4(L)], L = ( 1)–( 8), planar [PtCl2(L)], L = ( 1), ( 2), ( 3), ( 5), and neutral, five-coordinate [RhCl(cod)(L)], L = ( 2), ( 4), ( 6), are reported and trends in the spectroscopic data are discussed in terms of the ligand donor properties. Crystal structures of ( 3) and [Mo(CO)4( 3)] reveal significant structural changes occur upon coordination, and these are also reflected in the solution NMR spectroscopic parameters.

Changes in the C–Sb–C angles and C–Sb bond distances upon coordination of ( 3) are discussed in term of increased s/p orbital mixing. Air oxidation of ( 1) forms a very unusual stibine oxide, the structure of which shows a distorted Sb4O4 cubane core (bridging O atoms) with two orthogonal naphthalene units.

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Published date: 2008

Identifiers

Local EPrints ID: 146969
URI: http://eprints.soton.ac.uk/id/eprint/146969
ISSN: 0300-9246
PURE UUID: 21bb4a39-a2e2-44b5-bc9d-b752a4a30770
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 23 Apr 2010 08:36
Last modified: 08 Oct 2019 00:56

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Contributors

Author: Marek Jura
Author: William Levason ORCID iD
Author: Gillian Reid ORCID iD
Author: Michael Webster

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