Elucidating the Link between NMR Chemical Shifts and Electronic Structure in d(0) Olefin Metathesis Catalysts

Journal of the American Chemical Society
Stéphanie HalbertOdile Eisenstein

Abstract

The nucleophilic carbon of d(0) Schrock alkylidene metathesis catalysts, [M] = CHR, display surprisingly low downfield chemical shift (δiso) and large chemical shift anisotropy. State-of-the-art four-component relativistic calculations of the chemical shift tensors combined with a two-component analysis in terms of localized orbitals allow a molecular-level understanding of their orientations, the magnitude of their principal components (δ11 > δ22 > δ33) and associated δiso. This analysis reveals the dominating influence of the paramagnetic contribution yielding a highly deshielded alkylidene carbon. The largest paramagnetic contribution, which originates from the coupling of alkylidene σMC and π*MC orbitals under the action of the magnetic field, is analogous to that resulting from coupling σCC and π*CC in ethylene; thus, δ11 is in the MCH plane and is perpendicular to the MC internuclear direction. The higher value of carbon-13 δiso in alkylidene complexes relative to ethylene is thus due to the smaller energy gap between σMC and π*MC vs this between σCC and π*CC in ethylene. This effect also explains why the highest value of δiso is observed for Mo and the lowest for Ta, the values for W and Re being in between. In the prese...Continue Reading

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