Ligand exchange and stereodynamics in the cationic palladium(LL)–π-allyl complex of 2,2′-bis(pyridyl)-1,1′-binaphthalene, a novel atropisomeric N,N-ligand

Jonathan P. H. Charmant; Ian A. Fallis; Neil J. Hunt; Guy C. Lloyd-Jones; Martin Murray; Thorsten Nowak

doi:10.1039/B000651N

Ligand exchange and stereodynamics in the cationic palladium(LL)–π-allyl complex of 2,2′-bis(pyridyl)-1,1′-binaphthalene, a novel atropisomeric N,N-ligand

Jonathan P. H. Charmant,^a Ian A. Fallis,^a Neil J. Hunt,^a Guy C. Lloyd-Jones,*^a Martin Murray^a and Thorsten Nowak^a

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* Corresponding authors

^a School of Chemistry, Cantock’s Close, Bristol, UK
E-mail: guy.lloyd-jones@bris.ac.uk

^b School of Chemistry, University of Wales at Cardiff, PO Box 912, Cardiff, UK

^c AstraZeneca Pharmaceuticals, Mereside, Alderley Park, Macclesfield, Cheshire, UK

Abstract

Racemic 2,2′-bis(pyridin-2-yl)-1,1′-binaphthalene (±)-6 was prepared in four synthetic steps from 2-naphthol. Resolution of the novel atropisomeric ligand 6 was effected by repeated preparation, recrystallisation and then liberation of the bis-tartrate salt (D and L). This affords both enantiomers of 6 (>96% enantiomeric excess, ee) whose absolute configurations were assigned by CD. The ligand 6 is stable towards racemisation (ΔG^‡_rac > 167 kJ mol⁻¹) and the structure was confirmed by single crystal X-ray diffraction of the complex [ZnCl₂(6)]. The structure and stereodynamics of the complex [Pd(η³-C₃H₅)(6)][OTf] (OTf = O₃SCF₃) which comprises a C₂-symmetric ligand bound via Pd to a non-C₂-symmetric allyl fragment was studied in detail in solution by 1-D and 2-D ¹H NMR and in the solid state by single crystal X-ray diffraction. Apparent stereodynamic processes of the allyl ligand, as detected in solution by NMR, are shown to arise from ligand 6 stereodynamics and exchange. The ligand 6 represents the first compound/building block for a series of enantiomerically pure N,N-ligands that may be of utility in supramolecular co-ordination chemistry and in asymmetric catalysis.

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DOI: https://doi.org/10.1039/B000651N
Article type: Paper
Submitted: 24 Jan 2000
Accepted: 04 Apr 2000
First published: 04 May 2000

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J. Chem. Soc., Dalton Trans., 2000, 1723-1732

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Ligand exchange and stereodynamics in the cationic palladium(LL)–π-allyl complex of 2,2′-bis(pyridyl)-1,1′-binaphthalene, a novel atropisomeric N,N-ligand

J. P. H. Charmant, I. A. Fallis, N. J. Hunt, G. C. Lloyd-Jones, M. Murray and T. Nowak, J. Chem. Soc., Dalton Trans., 2000, 1723 DOI: 10.1039/B000651N

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Journal of the Chemical Society, Dalton Transactions

Ligand exchange and stereodynamics in the cationic palladium(LL)–π-allyl complex of 2,2′-bis(pyridyl)-1,1′-binaphthalene, a novel atropisomeric N,N-ligand

Abstract

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Ligand exchange and stereodynamics in the cationic palladium(LL)–π-allyl complex of 2,2′-bis(pyridyl)-1,1′-binaphthalene, a novel atropisomeric N,N-ligand

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