Anion Control of Lanthanoenediyne Cyclization

A suite of lanthanoenediyne complexes of the form Ln(macrocycle)X₃ (Ln = La³⁺, Ce³⁺, Eu³⁺, Gd³⁺, Tb³⁺, Lu³⁺; X = NO₃^-, Cl^-, OTf^-) was prepared by utilizing an enediyne-containing [2 + 2] hexaaza-macrocycle (2). The solid-state Bergman cyclization temperatures, measured via DSC, decrease with the denticity of X (bidentate NO₃^-, T = 267-292 °C; monodentate Cl^-, T = 238-262 °C; noncoordinating OTf^-, T = 170-183 °C). ¹³C NMR characterization shows that the chemical shifts of the acetylenic carbon atoms also rely on the anion identity. The alkyne carbon closest to the metal binding site, C_A, exhibits a Δδ > 3 ppm downfield shift, while the more distal alkyne carbon, C_B, displays a concomitant Δδ ≤ 2.5 ppm upfield shift, reflecting a depolarization of the alkyne on metal inclusion. For all metals studied, the degree of perturbation follows the trend 2 < NO₃^- < Cl^- < OTf^-. This belies a greater degree of electronic rearrangement in the coordinated macrocycle as the denticity of X and its accompanying shielding of the metal's Lewis acidity decrease. Computationally modeled structures of LnX₃ show a systematic increase in the lanthanide-2 coordination number (CN_La-mc = 2 (NO₃^-), 4 (Cl^-), 5 (H₂O, model for OTf^-)) and a decrease in the mean Ln-N bond length (La-N_average = 2.91 Å (NO₃^-), 2.78 Å (Cl^-), 2.68 Å (H₂O)), further suggesting that a decrease in the anion coordination number correlates with an increase in the metal-macrocycle interaction. Taken together, these data illustrate a Bergman cyclization landscape that is influenced by the bonding of metal to an enediyne ligand but whose reaction barrier is ultimately dominated by the coordinating ability of the accompanying anion.