Fluxional rhenium(I) tricarbonyl halide complexes of pyrazolylpyridine ligands. A detailed nuclear magnetic resonance investigation
- 1 January 1994
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 7,p. 1079-1090
- https://doi.org/10.1039/dt9940001079
Abstract
2,6-Bis(pyrazol-1-yl)pyridine (bppy) reacted with pentacarbonylhalogenorhenium(I) complexes under mild conditions to form stable octahedral complexes of type fac-[ReX(CO)3(bppy)](X = Cl, Br or I) in which bppy acts as a bidentate chelate ligand. In solution these tricarbonyl complexes are fluxional with bppy oscillating between equivalent bidentate bonding modes by a twist mechanism involving the breaking/making of two Re–N bonds. 2,6-Bis(3,5-dimethylpyrazol-1-yl)pyridine (tmbppy) and 2-(3, 5-dimethylpyrazol-1-yl)-6-(pyrazol-1-yl)pyridine (dmbppy) formed analogous fluxional complexes. The 1,4-Re–N metallotropic shifts of [ReX(CO)3(dmbppy)] interconvert chemically distinct complexes with different solution populations. Under more severe reaction conditions the complex cis-[ReBr(CO)2(tmbppy)] was formed in which the ligand adopts its more usual terdentate behaviour. Rates and activation energies of these ‘tick-lock’ twist fluxions have been investigated by one- and two-dimensional NMR methods. Activation energies are dependent on the relative donor strengths of the N atoms, with magnitudes of ΔG‡(298.15 K) being 55–56 (bppy), ≈69 (dmbppy) and 70–77 kJ mol–1(tmbppy).Keywords
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