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, Damian Ezequiel, Di Salvo, Florencia, González Lebrero, Mariano Camilo, Doctorovich, Fabio Ariel, Estrin, Dario Ariel
Publicado:	2005
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:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v44_n15_p5286_Bikiel 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	paper:paper_00201669_v44_n15_p5286_Bikiel
record_format	dspace
spelling	paper:paper_00201669_v44_n15_p5286_Bikiel2023-06-08T14:40:33Z Solvation and structure of LiAIH4 in ethereal solvents Bikiel, Damian Ezequiel Di Salvo, Florencia González Lebrero, Mariano Camilo Doctorovich, Fabio Ariel Estrin, Dario Ariel 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. 2005 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v44_n15_p5286_Bikiel 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, Damian Ezequiel Di Salvo, Florencia González Lebrero, Mariano Camilo Doctorovich, Fabio Ariel Estrin, Dario Ariel 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.
author	Bikiel, Damian Ezequiel Di Salvo, Florencia González Lebrero, Mariano Camilo Doctorovich, Fabio Ariel Estrin, Dario Ariel
author_facet	Bikiel, Damian Ezequiel Di Salvo, Florencia González Lebrero, Mariano Camilo Doctorovich, Fabio Ariel Estrin, Dario Ariel
author_sort	Bikiel, Damian Ezequiel
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
publishDate	2005
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v44_n15_p5286_Bikiel http://hdl.handle.net/20.500.12110/paper_00201669_v44_n15_p5286_Bikiel
work_keys_str_mv	AT bikieldamianezequiel solvationandstructureofliaih4inetherealsolvents AT disalvoflorencia solvationandstructureofliaih4inetherealsolvents AT gonzalezlebreromarianocamilo solvationandstructureofliaih4inetherealsolvents AT doctorovichfabioariel solvationandstructureofliaih4inetherealsolvents AT estrindarioariel solvationandstructureofliaih4inetherealsolvents
_version_	1768544670993874944

Solvation and structure of LiAIH4 in ethereal solvents

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