Theoretical and experimental study on a spirocyclic diethyleneglycol silicon complex
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| Format: | Artículo científico |
| Langue: | en |
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Sociedad Química de México
2006
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| _version_ | 1876472780778635264 |
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| author | J. Oscar C. Jiménez |
| author_facet | J. Oscar C. Jiménez |
| contents | Theoretical and experimental study on a spirocyclic diethyleneglycol silicon complex J. Oscar C. Jiménez Juvencio Robles Manuel Villanueva Gerardo González García M. Carmen Salazar Hernández Marco A. Leyva Ramírez Armando Ramírez Monroy Jorge Cervantes J. Alfredo Gutiérrez Multidisciplinaria (Ciencias Naturales y Exactas) Silicon Fukui function Diethyleneglycol Hypervalent compounds Density functional calculations In this paper a joint theoretical and experimental studyexamines the ability of diethyleneglycol as a ligand to form siliconcomplexes. Due to the known oxophilia of the silicon atom, it wouldbe expected that in the reaction of this tridentate O,O,O-donor-ligandwith a reagent such as SiCl4, the corresponding bis-chelate, hexacoordinatedneutral silicon complex may be formed. However, a spirocyclictetracoordinated silicon bis-chelate complex was isolated andno evidence of formation of any hypervalent alkoxysilane wasobserved. The tetracoordinated compound, 1,4,7,9,12,15-Hexaoxa-8-silaspiro[7.7]pentadecane (8CI,9CI), was crystallized in hexanes froman extract of the product of the aforementioned reaction in methylenechloride and its crystal structure has been determined by X-ray diffraction(C8H16O6Si; orthorhombic; a = 9.2892(3), b = 9.5845(3), c =12.3748(4) Å; space group P212121; Z = 4). From the same reaction,two other oligomeric tetracoordinated silicon compounds weredetected spectroscopically. Furthermore, Density Functional calculationsat the BP86/TZ2P level were performed for the bis-chelate compound.We obtained the condensed Fukui functions as well as theoreticalNMR chemical shifts to rationalize why the diethyleneglycolacts only as a dianionic, bidentate ligand towards silicon. Our DFTresults indicate that the tetracoordinated Si complex is a stable molecule(minimum energy point) whereas the hexacoordinated species isa first-order saddle point (transition state). These results are in agreementand rationalize the experimental findings 2006 artículo científico 1870-249X https://www.redalyc.org/articulo.oa?id=47550408 en http://www.redalyc.org/revista.oa?id=475 Journal of the Mexican Chemical Society application/pdf Sociedad Química de México Journal of the Mexican Chemical Society (México) Num.4 Vol.50 |
| format | Artículo científico |
| id | redalyc_47550408 |
| institution | Redalyc |
| language | en |
| publishDate | 2006 |
| publisher | Sociedad Química de México |
| spellingShingle | Theoretical and experimental study on a spirocyclic diethyleneglycol silicon complex J. Oscar C. Jiménez Multidisciplinaria (Ciencias Naturales y Exactas) Silicon Fukui function Diethyleneglycol Hypervalent compounds Density functional calculations Theoretical and experimental study on a spirocyclic diethyleneglycol silicon complex J. Oscar C. Jiménez Juvencio Robles Manuel Villanueva Gerardo González García M. Carmen Salazar Hernández Marco A. Leyva Ramírez Armando Ramírez Monroy Jorge Cervantes J. Alfredo Gutiérrez Multidisciplinaria (Ciencias Naturales y Exactas) Silicon Fukui function Diethyleneglycol Hypervalent compounds Density functional calculations In this paper a joint theoretical and experimental studyexamines the ability of diethyleneglycol as a ligand to form siliconcomplexes. Due to the known oxophilia of the silicon atom, it wouldbe expected that in the reaction of this tridentate O,O,O-donor-ligandwith a reagent such as SiCl4, the corresponding bis-chelate, hexacoordinatedneutral silicon complex may be formed. However, a spirocyclictetracoordinated silicon bis-chelate complex was isolated andno evidence of formation of any hypervalent alkoxysilane wasobserved. The tetracoordinated compound, 1,4,7,9,12,15-Hexaoxa-8-silaspiro[7.7]pentadecane (8CI,9CI), was crystallized in hexanes froman extract of the product of the aforementioned reaction in methylenechloride and its crystal structure has been determined by X-ray diffraction(C8H16O6Si; orthorhombic; a = 9.2892(3), b = 9.5845(3), c =12.3748(4) Å; space group P212121; Z = 4). From the same reaction,two other oligomeric tetracoordinated silicon compounds weredetected spectroscopically. Furthermore, Density Functional calculationsat the BP86/TZ2P level were performed for the bis-chelate compound.We obtained the condensed Fukui functions as well as theoreticalNMR chemical shifts to rationalize why the diethyleneglycolacts only as a dianionic, bidentate ligand towards silicon. Our DFTresults indicate that the tetracoordinated Si complex is a stable molecule(minimum energy point) whereas the hexacoordinated species isa first-order saddle point (transition state). These results are in agreementand rationalize the experimental findings 2006 artículo científico 1870-249X https://www.redalyc.org/articulo.oa?id=47550408 en http://www.redalyc.org/revista.oa?id=475 Journal of the Mexican Chemical Society application/pdf Sociedad Química de México Journal of the Mexican Chemical Society (México) Num.4 Vol.50 |
| title | Theoretical and experimental study on a spirocyclic diethyleneglycol silicon complex |
| topic | Multidisciplinaria (Ciencias Naturales y Exactas) Silicon Fukui function Diethyleneglycol Hypervalent compounds Density functional calculations |
| url | https://www.redalyc.org/articulo.oa?id=47550408 |