The η3-Furfuryl Ligand: Plausible Catalytic Intermediates and Heterocyclic η3-Benzyl Analogues with Superior Binding Ability.

Five-membered heterocyclic analogues of the well-known η3-allyl and η3-benzyl ligands, e.g., η3-thienyl and η3-furfuryl, have been proposed as catalytic intermediates, yet are poorly understood and have never been structurally confirmed. Herein we characterize an η3-furfuryl complex by multinuclear NMR spectroscopy and crystallography and offer a computational survey of allyl and allyl-like ligands. Crystallographically and computationally, we show that the η3-furfuryl ligand may bind more strongly than corresponding η3-benzyl ligands and is plausible as a catalytic intermediate. Five-membered heterocyclic analogues of the well-known η3-allyl and η3-benzyl ligands, e.g., η3-thienyl and η3-furfuryl, have been proposed as catalytic intermediates, yet are poorly understood and have never been structurally confirmed. Herein we characterize an η3-furfuryl complex by multinuclear NMR spectroscopy and crystallography and offer a computational survey of allyl and allyl-like ligands. Crystallographically and computationally, we show that the η3-furfuryl ligand may bind more strongly than corresponding η3-benzyl ligands and is plausible as a catalytic intermediate. [ABSTRACT FROM AUTHOR]