Your browser doesn't support javascript.
Reversible gas uptake by a nonporous crystalline solid involving multiple changes in covalent bonding.
J Am Chem Soc ; 129(50): 15606-14, 2007 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-18034480
Hydrogen chloride gas (HCl) is absorbed (and reversibly released) by a nonporous crystalline solid, [CuCl2(3-Clpy)2] (3-Clpy = 3-chloropyridine), under ambient conditions leading to conversion from the blue coordination compound to the yellow salt (3-ClpyH)2[CuCl4]. These reactions require substantial motions within the crystalline solid including a change in the copper coordination environment from square planar to tetrahedral. This process also involves cleavage of the covalent bond of the gaseous molecules (H-Cl) and of coordination bonds of the molecular solid compound (Cu-N) and formation of N-H and Cu-Cl bonds. These reactions are not a single-crystal-to-single-crystal transformation; thus, the crystal structure determinations have been performed using X-ray powder diffraction. Importantly, we demonstrate that these reactions proceed in the absence of solvent or water vapor, ruling out the possibility of a water-assisted (microscopic recrystallization) mechanism, which is remarkable given all the structural changes needed for the process to take place. Gas-phase FTIR spectroscopy has permitted us to establish that this process is actually a solid-gas equilibrium, and time-resolved X-ray powder diffraction (both in situ and ex situ) has been used for the study of possible intermediates as well as the kinetics of the reaction.





Coleções: Bases de dados internacionais Base de dados: MEDLINE Assunto principal: Gases Idioma: Inglês Revista: J Am Chem Soc Ano de publicação: 2007 Tipo de documento: Artigo País de afiliação: Reino Unido