An NMR study of the solution conformations of di(tertiary phosphine) complexes of orthopalladated 1-phenyl-1-(N,N-dimethylamino)ethane

McFarlane, William, Swarbrick A, James and Bookham, Jonathan (1998) An NMR study of the solution conformations of di(tertiary phosphine) complexes of orthopalladated 1-phenyl-1-(N,N-dimethylamino)ethane. Journal of the Chemical Society - Dalton Transactions (19). pp. 3233-3238. ISSN 1472-7773

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Abstract

NOE intensities derived primarily from 2-D NMR ROESY spectra were used to study the solution conformations of the chelate rings of the (R)- and (S)-[1-phenyl-1-(N,N-dimethylamino)ethane][(2R,3R)-bis(diphenylphosphino)- butane]palladium(II) cations, 3 and 4. In each, the diphosphine ring adopts a conformation with both N-methyl groups equatorial owing to potential unfavourable trans-annular methyl-phenyl interactions in the alternative conformation with axial methyl groups. For the orthometallated chelate ring the population of the conformer with C-methyl equatorial is less than 10% in 4, but is close to 55% in 3. This contrasting behaviour is attributed to interannular steric interactions between the N-methyl and the P-phenyl groups which also lead to a weakening of the Pd-N bond in 3 and can account for the enantioselectivity of the orthopalladated 1-phenyl-1-(N,N-dimethylamino)ethane moiety when used as a resolving agent.

Item Type:	Article
Subjects:	F100 Chemistry
Department:	Faculties > Health and Life Sciences > Applied Sciences
Depositing User:	Becky Skoyles
Date Deposited:	29 Jan 2015 13:40
Last Modified:	12 Oct 2019 17:29
URI:	http://nrl.northumbria.ac.uk/id/eprint/20033

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