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Assignment of phosphorus NMR parameters to absolute configurations in chiral phosphorus sulfide cage compounds, using Ab initio methods

Lookup NU author(s): Dr Bruce Tattershall


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The closo cage molecules α- and β-P4S 3(μ-NCH(Me)Ph) were modelled at the RHF/3-21G* and MPW1PW91/DZVP levels. For each, the conformational space corresponding to rotation about the C-N bond was explored, and relative average electronic energies were calculated. The β-isomer was more stable than the α-isomer by 10.7 kJ mol-1, according to the DFT calculations, in contrast to the unsubstituted model compounds α- and β-P 4S3(μ-NH), where the α-isomer was more stable. GIAO calculations of phosphorus isotropic NMR shieldings, in the rotamers, led to relative average chemical shifts in the diastereomers. Comparison with experimental chemical shift differences gave an assignment to absolute configuration for α-P4S3(μ-NCH(Me)Ph), which agreed with the assignment obtained by comparing calculated relative diastereomer stability with observations. For β-P4S 3(μ-NCH(Me)Ph), the GIAO calculations allowed relative assignment of observed chemical shifts to the nitrogen bridgehead phosphorus atoms. © 2005 WILEY-VCH Verlag GmbH & Co.

Publication metadata

Author(s): Tattershall BW

Publication type: Article

Publication status: Published

Journal: Zeitschrift fur Anorganische und Allgemeine Chemie

Year: 2005

Volume: 631

Issue: 9

Pages: 1627-1632

Print publication date: 01/07/2005

ISSN (print): 0044-2313

ISSN (electronic): 1521-3749

Publisher: Wiley


DOI: 10.1002/zaac.200500016


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