A detailed NMR study of the solution stereodynamics in tricarbonylrhenium(I) halide complexes of the non-racemic chiral ligand 2,6-bis[(4R,5R)-4,5-dimethyl-1,3-dioxolan-2-yl]pyridine (L¹) and the molecular structure of fac-[ReBr(CO)₃(L¹)]
Heard, Peter J, King, Paul M, Bain, Alex D, Hazendonk, Paul and Tocher, Derek A (1999) A detailed NMR study of the solution stereodynamics in tricarbonylrhenium(I) halide complexes of the non-racemic chiral ligand 2,6-bis[(4R,5R)-4,5-dimethyl-1,3-dioxolan-2-yl]pyridine (L¹) and the molecular structure of fac-[ReBr(CO)₃(L¹)].
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Abstract
1 Tricarbonylrhenium(I) halide complexes of the non-racemic chiral ligand 2,6-bis[(4R, 5R)-dimethyl-1,3-dioxan-2-yl]pyridine (L¹), namely fac-[ReX(CO)₃(L¹)] (X = Cl, Br or I), have been prepared. In these complexes the ligand is bound in a bidentate fashion, with the N atom of the pyridine ring and an O atom of one of the acetal rings co-ordinated to the octahedral metal centre. The bidentate mode is confirmed by the X-ray structure of fac-[ReBr(CO)₃(L¹)]. There are four possible diastereoisomers, depending on the configuration at the metal centre and at the acetal-carbon atom of the co-ordinated ring; the X-ray structure of fac-[ReBr(CO)₃(L¹)] shows that the SR diastereoisomer is present in the solid state. In solution, three of the four possible diastereoisomers are observed, namely SR, RR and RS; their relative populations are in the order SR > RR > SS. Above ambient temperature the complexes are stereochemically non-rigid. The fluxional kinetics have been measured by a combination of standard band shape analysis and selective inversion experiments. Two distinct processes are present: an acetal ring flip and exchange of the pendant and co-ordinated acetal rings. The latter process occurs via two independent mechanisms, namely tick-tock and rotation pathways. The activation energies for the stereodynamics are in the ranges 72 – 73 kJ mol⁻¹ (tick-tock), 77 – 78 kJ mol⁻¹ (acetal ring flip) and 83 – 90 kJ mol⁻¹ (rotation) at 298 K.
| Item Type: | Article |
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| Additional Information: | Copyright © 1999 RCS, and reproduced here by permission of The Royal Society of Chemistry (RSC).This is the author's final draft after peer review. The article was published in Heard, P. J., King, P. M., Bain, A.D., Hazendonk, P., and Tocher, D. A. (1999) 'A detailed NMR study of the solution stereodynamics in tricarbonylrhenium(I) halide complexes of the non-racemic chiral ligand 2,6-bis[(4R,5R)-4,5-dimethyl-1,3-dioxolan-2-yl]pyridine (L¹) and the molecular structure of fac-[ReBr(CO)'(L¹)]'. Dalton Transactions, 4495-4501 by the Royal Society of Chemistry and is available online at http://dx.doi.org/10.1039/a904026i |
| Keywords: | Rhenium(I) complexe, Dynamic NMR spectroscopy, Chrial acetal ligands, Chiral organometallic complexes |
| Divisions: | ?? GlyndwrUniversity ?? |
| Depositing User: | ULCC Admin |
| Date Deposited: | 05 Oct 2011 09:13 |
| Last Modified: | 11 Dec 2017 20:05 |
| URI: | https://wrexham.repository.guildhe.ac.uk/id/eprint/149 |
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