Probing organometallic structure and reactivity by transition metal NMR spectroscopy†

Abstract

Transition metal NMR chemical shifts are readily measured by modern 1D and 2D pulse techniques and serve as a probe into electronic and steric effects of ligands and substituents in metal complexes. Quantitative correlations of metal chemical shifts with reaction rates and catalytic activities, both experimental and as a result of quantum chemical calculations, give new mechanistic insights and permit reactivity predictions and a screening of homogeneous catalysts. A variety of such examples involving the spin-1/2 nuclei ⁵⁷Fe, ¹⁰³Rh, and ¹⁸⁷Os as well as the quadrupolar nuclei ⁵¹V, ⁵³Cr, ⁵⁵Mn, ⁵⁹Co, and ⁹¹Zr are discussed.