Ligand Exchange Processes on Solvated Beryllium Cations, VI. Hydrogen Chalcogenide Exchange on [Be(Chelate)Sol2]2+ (Chelate: CH3-O-C2H4-O-CH3, CH3-S-C2H4-S-CH3, CH3-Se-C2H4-Se-CH3; Sol: H2O, H2S, H2Se)

• Published in: Zeitschrift für anorganische und allgemeine Chemie (1950) 2011-10, Vol.637 (12), p.1736-1740
• Main Authors: Walther, Markus, Dücker-Benfer, Carlos, Puchta, Ralph
• Format: Article
• Language: English
• Subjects: Beryllium; Density functional calculations; Ether; Quantum-chemical calculations; Solvent exchange
• ISSN: 0044-2313; 1521-3749
• DOI: 10.1002/zaac.201100312

Following work from Dehnicke et al. on the binding of Be2+ to crown ethers, solvent addition, and solvent exchange energies were calculated (B3LYP/6‐311+G**) for solvated beryllium complexes with bidentate ligands CH3–O–C2H4–O–CH3 [1,2‐bis(methoxy)ethane], CH3–S–C2H4–S–CH3 [1,2‐bis(methio)ethane], and CH3–Se–C2H4–Se–CH3 [1,2‐bis(methylselanyl)ethane], and H2O, H2S, and H2Se as solvents. All water exchange reactions for the different bidentate ligands show no variation, with energies of addition to the second coordination sphere of around –25 kcal·mol–1 and exchange activation energies of around 19 kcal·mol–1. Substituting water by H2S and H2Se in [(CH3–O–C2H4–O–CH3)Be(Solvent)2]2+ lowered the energy for addition of a solvent molecule in the second coordination sphere to –12 kcal·mol–1 and the exchange activation energy to 12 kcal·mol–1. All reaction mechanisms were found to be of the associative interchange (Ia) type.