Solvation and structure of LiAIH4 in ethereal solvents

The nature of the solute species present in ethereal solutions of LiAIH4 is of crucial importance for understanding the mechanisms for the reduction of ketones and other functional groups by LiAIH4. We have employed a combination of theoretical and experimental techniques to investigate the structur...

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Autores principales:	Bikiel, D.E., Di Salvo, F., González Lebrero, M.C., Doctorovich, F., Estrin, D.A.
Formato:	JOUR
Materias:	aluminum derivative aluminum lithium hydride dimethyl ether ether derivative furan derivative lithium derivative solvent tetrahydrofuran article chemical model chemical structure chemistry computer simulation solubility X ray crystallography Aluminum Compounds Computer Simulation Crystallography, X-Ray Furans Lithium Compounds Methyl Ethers Models, Chemical Models, Molecular Solubility Solvents
Acceso en línea:	http://hdl.handle.net/20.500.12110/paper_00201669_v44_n15_p5286_Bikiel
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	todo:paper_00201669_v44_n15_p5286_Bikiel
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spelling	todo:paper_00201669_v44_n15_p5286_Bikiel2023-10-03T14:16:55Z Solvation and structure of LiAIH4 in ethereal solvents Bikiel, D.E. Di Salvo, F. González Lebrero, M.C. Doctorovich, F. Estrin, D.A. aluminum derivative aluminum lithium hydride dimethyl ether ether derivative furan derivative lithium derivative solvent tetrahydrofuran article chemical model chemical structure chemistry computer simulation solubility X ray crystallography Aluminum Compounds Computer Simulation Crystallography, X-Ray Furans Lithium Compounds Methyl Ethers Models, Chemical Models, Molecular Solubility Solvents The nature of the solute species present in ethereal solutions of LiAIH4 is of crucial importance for understanding the mechanisms for the reduction of ketones and other functional groups by LiAIH4. We have employed a combination of theoretical and experimental techniques to investigate the structure of LiAIH4 in ethereal solutions. Using complexation agents, we measured the IR spectra of LiAIH4 and AIH4- in tetrahydrofuran (THF). Hybrid quantum-classical (QM-MM) simulations have also been carried out to compute the IR spectra of associated and dissociated LiAIH4 species and the free-energy profile for the dissociation process in solution. Our experimental estimate of the dissociation constant in THF is 0.021 ± 0.002, while the predicted computational value corresponding to a model dimethyl ether solvent is 0.001. The free-energy profile shows only one minimum corresponding to a contact ion pair at a Li-AI separation distance of 3.0 Å. These results are consistent with the fact that LiAIH4 is essentially associated in ethereal solutions forming contact ion pairs. © 2005 American Chemical Society. Fil:Bikiel, D.E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Di Salvo, F. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:González Lebrero, M.C. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Doctorovich, F. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Estrin, D.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00201669_v44_n15_p5286_Bikiel
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	aluminum derivative aluminum lithium hydride dimethyl ether ether derivative furan derivative lithium derivative solvent tetrahydrofuran article chemical model chemical structure chemistry computer simulation solubility X ray crystallography Aluminum Compounds Computer Simulation Crystallography, X-Ray Furans Lithium Compounds Methyl Ethers Models, Chemical Models, Molecular Solubility Solvents
spellingShingle	aluminum derivative aluminum lithium hydride dimethyl ether ether derivative furan derivative lithium derivative solvent tetrahydrofuran article chemical model chemical structure chemistry computer simulation solubility X ray crystallography Aluminum Compounds Computer Simulation Crystallography, X-Ray Furans Lithium Compounds Methyl Ethers Models, Chemical Models, Molecular Solubility Solvents Bikiel, D.E. Di Salvo, F. González Lebrero, M.C. Doctorovich, F. Estrin, D.A. Solvation and structure of LiAIH4 in ethereal solvents
topic_facet	aluminum derivative aluminum lithium hydride dimethyl ether ether derivative furan derivative lithium derivative solvent tetrahydrofuran article chemical model chemical structure chemistry computer simulation solubility X ray crystallography Aluminum Compounds Computer Simulation Crystallography, X-Ray Furans Lithium Compounds Methyl Ethers Models, Chemical Models, Molecular Solubility Solvents
description	The nature of the solute species present in ethereal solutions of LiAIH4 is of crucial importance for understanding the mechanisms for the reduction of ketones and other functional groups by LiAIH4. We have employed a combination of theoretical and experimental techniques to investigate the structure of LiAIH4 in ethereal solutions. Using complexation agents, we measured the IR spectra of LiAIH4 and AIH4- in tetrahydrofuran (THF). Hybrid quantum-classical (QM-MM) simulations have also been carried out to compute the IR spectra of associated and dissociated LiAIH4 species and the free-energy profile for the dissociation process in solution. Our experimental estimate of the dissociation constant in THF is 0.021 ± 0.002, while the predicted computational value corresponding to a model dimethyl ether solvent is 0.001. The free-energy profile shows only one minimum corresponding to a contact ion pair at a Li-AI separation distance of 3.0 Å. These results are consistent with the fact that LiAIH4 is essentially associated in ethereal solutions forming contact ion pairs. © 2005 American Chemical Society.
format	JOUR
author	Bikiel, D.E. Di Salvo, F. González Lebrero, M.C. Doctorovich, F. Estrin, D.A.
author_facet	Bikiel, D.E. Di Salvo, F. González Lebrero, M.C. Doctorovich, F. Estrin, D.A.
author_sort	Bikiel, D.E.
title	Solvation and structure of LiAIH4 in ethereal solvents
title_short	Solvation and structure of LiAIH4 in ethereal solvents
title_full	Solvation and structure of LiAIH4 in ethereal solvents
title_fullStr	Solvation and structure of LiAIH4 in ethereal solvents
title_full_unstemmed	Solvation and structure of LiAIH4 in ethereal solvents
title_sort	solvation and structure of liaih4 in ethereal solvents
url	http://hdl.handle.net/20.500.12110/paper_00201669_v44_n15_p5286_Bikiel
work_keys_str_mv	AT bikielde solvationandstructureofliaih4inetherealsolvents AT disalvof solvationandstructureofliaih4inetherealsolvents AT gonzalezlebreromc solvationandstructureofliaih4inetherealsolvents AT doctorovichf solvationandstructureofliaih4inetherealsolvents AT estrinda solvationandstructureofliaih4inetherealsolvents
_version_	1782028039265189888

Solvation and structure of LiAIH4 in ethereal solvents

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