Protonation and complexation properties of polyaromatic terdentate six-membered chelate ligands.
The successive protonation steps occurring in 2,2′;6′,2″-terpyridine (L1) are characterized by a strong affinity for the first entering proton (ΔG(connect)(H,L1) = −17 kJ/mol) followed by allosteric anticooperativity (ΔE(interaction)(H,H,L1) = 6 kJ/mol), a behavior mirrored by 2,6-bis(azaindolyl)pyridine (L2) despite the extension of the chelate ring size from five members (L1) to six members (L2; ΔG(connect)(H,L2) = −28 kJ/mol and ΔE(interaction)(H,H,L2) = 7 kJ/mol). On the contrary, 2,6-bis(8-quinolinyl)pyridine (L3) is less eager for the initial protonation (ΔG(connect)(H,L3) = −10 kJ/mol), but the fixation of a second proton in [H2L3]2+ is driven to completion by positive cooperativity (ΔE(interaction)(H,H,L3) = −5 kJ/mol). Because of its unusual ability to adopt a cis–cis conformation with a large affinity for the entering protons, L2 has been selected for exploring the reactivity of a terdentate fused six-membered chelate with labile metallic cations possessing increasing electrostatic factors along the series Mz+ = Li+ < Mg2+ ≈ Zn2+ < Y3+. Spectroscopic, thermodynamic, and structural studies demonstrate that covalency is crucial for stabilizing the complexes [Zn(L2)n]2+. With the highly charged Y3+ cation, hydrolysis drastically competes with ligand complexation, but anhydrous conditions restore sufficient selectivity for the successful coordination of neutral fused six-membered polyaromatic terdentate chelates with large 4f-block cations.
Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai E. Ansermet, CH-1211 Geneva 4, Switzerland.
Thi Nhu Y
TN
Hoang
Timothée
T
Lathion
Laure
L
Guénée
Emmanuel
E
Terazzi
Claude
C
Piguet