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Ligand Exchange Processes on Solvated Beryllium Cations, VI . Hydrogen Chalcogenide Exchange on [Be(Chelate)Sol 2 ] 2+ (Chelate: CH 3 –O–C 2 H 4 –O–CH 3 , CH 3 –S–C 2 H 4 –S–CH 3 , CH 3 –Se–C 2 H 4 –Se–CH 3 ; Sol: H 2 O, H 2 S, H 2 Se)
Author(s) -
Walther Markus,
DückerBenfer Carlos,
Puchta Ralph
Publication year - 2011
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201100312
Subject(s) - chemistry , denticity , coordination sphere , solvent , ligand (biochemistry) , beryllium , activation energy , chelation , inorganic chemistry , molecule , crystallography , medicinal chemistry , crystal structure , organic chemistry , biochemistry , receptor
Following work from Dehnicke et al. on the binding of Be 2+ to crown ethers, solvent addition, and solvent exchange energies were calculated (B3LYP/6‐311+G**) for solvated beryllium complexes with bidentate ligands CH 3 –O–C 2 H 4 –O–CH 3 [1,2‐bis(methoxy)ethane], CH 3 –S–C 2 H 4 –S–CH 3 [1,2‐bis(methio)ethane], and CH 3 –Se–C 2 H 4 –Se–CH 3 [1,2‐bis(methylselanyl)ethane], and H 2 O, H 2 S, and H 2 Se 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 H 2 S and H 2 Se in [(CH 3 –O–C 2 H 4 –O–CH 3 )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 (I a ) type.