Details

Autor(en) / Beteiligte

• D’Vries, Richard F
• de la Peña-O’Shea, Victor A
• Snejko, Natalia
• Iglesias, Marta
• Gutiérrez-Puebla, Enrique
• Monge, M. Angeles

Titel

H3O2 Bridging Ligand in a Metal–Organic Framework. Insight into the Aqua-Hydroxo↔Hydroxyl Equilibrium: A Combined Experimental and Theoretical Study

Ist Teil von

• Journal of the American Chemical Society, 2013-04, Vol.135 (15), p.5782-5792

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2013

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• A metal–organic framework (MOF) bearing the aqua-hydroxo species (O2H3)− in the framework, as well as the processes that govern the equilibrium aqua-hydroxo (O2H3)−↔hydroxyl (OH) in Sc-MOFs, are studied experimentally and theoretically. Computational studies were employed to determine the relative energies for the two compounds that coexist under certain hydrothermal conditions at pH < 2.8. The thermodynamically more stable [Sc3(3,5-DSB)2(μ-O2H3)(μ-OH)2(H2O)2] (from now on, (O 2 H 3 )Sc-MOF; 3,5-DSB = 3,5-disulfobenzoic acid) was obtained as a pure and stable phase. It was impossible to isolate [Sc3(3,5-DSB)2(μ-OH)3(H2O)4] as a pure phase, as it turned out to be the precursor of (O 2 H 3 )Sc-MOF. Additionally, a third compound that appears at pH between 3.5 and 4, [Sc3(3,5-DSB)(μ-OH)6(H2O)] and a fourth, [Sc(3,5-DSB)(Phen)(H2O)](H2O), in whose formula neither OH groups nor H3O2 – anions appear, are reported for comparative purposes. A study of the (O 2 H 3 )Sc-MOF electronic structure, and some heterogeneous catalytic tests in cyanosilylation of aldehydes reactions, are also reported.