Artículo
Bikiel, D.E.; Di Salvo, F.; González Lebrero, M.C.; Doctorovich, F.; Estrin, D.A. "Solvation and structure of LiAIH4 in ethereal solvents" (2005) Inorganic Chemistry. 44(15):5286-5292
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Abstract:
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.
Registro:
| Documento: | Artículo |
| Título: | Solvation and structure of LiAIH4 in ethereal solvents |
| Autor: | Bikiel, D.E.; Di Salvo, F.; González Lebrero, M.C.; Doctorovich, F.; Estrin, D.A. |
| Filiación: | Departamento de Quimica Inorganica, Analitica Y Quimica Fisica - INQUIMAE-CONICET, Facultad de Ciencias Exactas Y Naturales, Pabellón 2, C1428EHA, Buenos Aires, Argentina |
| Palabras clave: | 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 |
| Año: | 2005 |
| Volumen: | 44 |
| Número: | 15 |
| Página de inicio: | 5286 |
| Página de fin: | 5292 |
| DOI: | http://dx.doi.org/10.1021/ic050330q |
| Título revista: | Inorganic Chemistry |
| Título revista abreviado: | Inorg. Chem. |
| ISSN: | 00201669 |
| CODEN: | INOCA |
| CAS: | aluminum lithium hydride, 16853-85-3; dimethyl ether, 115-10-6; tetrahydrofuran, 109-99-9; Aluminum Compounds; dimethyl ether, 115-10-6; Furans; lithium aluminum hydride, 16853-85-3; Lithium Compounds; Methyl Ethers; Solvents; tetrahydrofuran, 109-99-9 |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v44_n15_p5286_Bikiel |
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Citas:
---------- APA ----------
Bikiel, D.E., Di Salvo, F., González Lebrero, M.C., Doctorovich, F. & Estrin, D.A. (2005) . Solvation and structure of LiAIH4 in ethereal solvents. Inorganic Chemistry, 44(15), 5286-5292.http://dx.doi.org/10.1021/ic050330q
---------- CHICAGO ----------
Bikiel, D.E., Di Salvo, F., González Lebrero, M.C., Doctorovich, F., Estrin, D.A. "Solvation and structure of LiAIH4 in ethereal solvents" . Inorganic Chemistry 44, no. 15 (2005) : 5286-5292.http://dx.doi.org/10.1021/ic050330q
---------- MLA ----------
Bikiel, D.E., Di Salvo, F., González Lebrero, M.C., Doctorovich, F., Estrin, D.A. "Solvation and structure of LiAIH4 in ethereal solvents" . Inorganic Chemistry, vol. 44, no. 15, 2005, pp. 5286-5292.http://dx.doi.org/10.1021/ic050330q
---------- VANCOUVER ----------
Bikiel, D.E., Di Salvo, F., González Lebrero, M.C., Doctorovich, F., Estrin, D.A. Solvation and structure of LiAIH4 in ethereal solvents. Inorg. Chem. 2005;44(15):5286-5292.http://dx.doi.org/10.1021/ic050330q
