Please use this identifier to cite or link to this item: https://doi.org/10.1021/ic0509579
Title: Stereochemical investigations of a novel class of chiral phosphapalladacycle complexes derived from 1-[(2,5-dimethyl)phenyl] ethyldiphenylphosphine
Authors: Ng, J.K.-P.
Li, Y.
Tan, G.-K.
Koh, L.-L. 
Vittal, J.J. 
Leung, P.-H.
Issue Date: 26-Dec-2005
Source: Ng, J.K.-P., Li, Y., Tan, G.-K., Koh, L.-L., Vittal, J.J., Leung, P.-H. (2005-12-26). Stereochemical investigations of a novel class of chiral phosphapalladacycle complexes derived from 1-[(2,5-dimethyl)phenyl] ethyldiphenylphosphine. Inorganic Chemistry 44 (26) : 9874-9886. ScholarBank@NUS Repository. https://doi.org/10.1021/ic0509579
Abstract: The phosphapalladacycle derived from 1-(2′,5′-dimethylphenyl) ethyldiphenylphosphine has been prepared in the optically active and racemic forms. The phosphine was synthesized as a racemate by the treatment of 1-chloro-1-(2′,5′-dimethylphenyl)ethane with sodium diphenylphosphide in THF. The racemic phosphapalladacycle was subsequently obtained as the chloro-bridged dimer by the treatment of the phosphine with palladium(II) acetate followed by anion metathesis with lithium chloride. Alternatively, the phosphine could be optically resolved via metal complexation using (R,R)-bis(μ-chloro)bis{1-[1-(N,N-dimethylamino)ethyl]naphthyl-C 2,N}dipalladium(II) as the resolving agent. An efficient separation of the resulting diastereomeric complexes was achieved by silica gel chromatography. The obtained optically resolved diastereomers were next subject to chemoselective removal of the (R)-N,N-(dimethylamino)-1-(1-naphthyl) ethylaminate auxiliary by treatment with concentrated hydrochloric acid. This process yielded the binuclear dimer complexes containing the resolved η 1-P ligand. Cyclopalladation of the coordinated phosphine could next be performed by treatment of its η 1-P binuclear dimer with silver(I) hexafluorophosphate(V) in a dichloromethane/water mixture followed by treatment with lithium chloride, giving rise to a pair of optically pure enantiomeric dimers with [α] D -322 and +319° in CH 2Cl 2. Despite the possibilities of the phosphine to attain a five- membered structure by ortho-palladation or a six-membered ring formation by aliphatic C-H bond activation, only the former was observed. X-ray crystallographic data of the meso dimer and an acetylacetonate derivative indicated that the phosphapalladacycle α-C* methyl substituent was axially located. The 2-D 1H- 1H ROESY spectrum of the acetylacetonate derivative further revealed that the phosphapalladacycle was conformationally rigid in CDCl 3. © 2005 American Chemical Society.
Source Title: Inorganic Chemistry
URI: http://scholarbank.nus.edu.sg/handle/10635/94874
ISSN: 00201669
DOI: 10.1021/ic0509579
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