Triarylsilanolates are privileged ancillary ligands for molybdenum alkylidyne catalysts for alkyne metathesis but lead to disappointing results and poor stability in the tungsten series. 1 H,183 W heteronuclear multiple bond correlation spectroscopy, exploiting a favorable 5 J-coupling between the 183 W center and the peripheral protons on the alkylidyne cap, revealed that these ligands upregulate the Lewis acidity to an extent that the tungstenacyclobutadiene formed in the initial [2+2] cycloaddition step is over-stabilized and the catalytic turnover brought to a halt. Guided by the 183 W NMR shifts as a proxy for the Lewis acidity of the central atom and by an accompanying chemical shift tensor analysis of the alkylidyne unit, the ligand design was revisited and a more strongly π-donating all-alkoxide ligand prepared. The new expanded chelate complex has a tempered Lewis acidity and outperforms the classical Schrock catalyst, carrying monodentate tert-butoxy ligands, in terms of rate and functional-group compatibility.
Keywords: NMR spectroscopy; ligand design; metathesis; structure elucidation; tungsten.
© 2020 The Authors. Published by Wiley-VCH GmbH.