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Title: Optical resolution and the stereoelectronic properties of chelating (±)-[(methylsulfinyl)methyl]diphenylphosphine
Authors: Leung, P.-H. 
Quek, G.H. 
Lang, H.
Liu, A.M.
Mok, K.F. 
White, A.J.P.
Williams, D.J.
Rees, N.H.
McFarlane, W.
Issue Date: 21-May-1998
Citation: Leung, P.-H.,Quek, G.H.,Lang, H.,Liu, A.M.,Mok, K.F.,White, A.J.P.,Williams, D.J.,Rees, N.H.,McFarlane, W. (1998-05-21). Optical resolution and the stereoelectronic properties of chelating (±)-[(methylsulfinyl)methyl]diphenylphosphine. Journal of the Chemical Society - Dalton Transactions (10) : 1639-1643. ScholarBank@NUS Repository.
Abstract: Optical resolution of the asymmetric chelating agent (±)-Ph2PCH2S(O)Me has been achieved via fractional crystallization of a pair of diastereomeric palladium(II) cationic complexes containing the sulfinyl-substituted ligand and ortho-metallated (S)-[1-(dimethylamino)ethyl]naphthalene. The X-ray structural analysis of the perchlorate salt of the less-soluble diastereomer confirmed that the sulfinyl-substituted phosphine co-ordinated to the palladium via phosphorus and oxygen with the non-co-ordinated sulfur having an R absolute configuration. An unusual electronic repulsion is observed between palladium and the non-bonded sulfur lone pair thus directing the methyl substituent on sulfur to a sterically unfavored axial position. Furthermore, a two-dimensional rotating frame Overhauser enhancement 1H NMR study of the complex in CDCl3 confirmed that this intramolecular electronic interaction outweighs the general steric considerations in solution. Optically pure (R)-(+)-Ph2PCH2-S(O)Me was displaced from the resolving palladium complex with 1,2-bis(diphenylphosphino)ethane.
Source Title: Journal of the Chemical Society - Dalton Transactions
ISSN: 03009246
Appears in Collections:Staff Publications

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