Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis
Abstract The effect of calixarene ligand symmetry, as dictated by lower-rim substitution pattern, on the coordination to a Ti(IV) cation is assessed in solution and when grafted on $ SiO_{2} $, and its effect on epoxidation catalysis by Ti(IV)-calixarene grafted on $ SiO_{2} $ is investigated. $ C_{...
Ausführliche Beschreibung
Autor*in: |
Grosso-Giordano, Nicolás A. [verfasserIn] Solovyov, Andrew [verfasserIn] Hwang, Sonjong [verfasserIn] Katz, Alexander [verfasserIn] |
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Format: |
E-Artikel |
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Sprache: |
Englisch |
Erschienen: |
2016 |
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Schlagwörter: |
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Übergeordnetes Werk: |
Enthalten in: Topics in catalysis - Bussum : Baltzer, 1994, 59(2016), 13-14 vom: 10. Juni, Seite 1110-1122 |
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Übergeordnetes Werk: |
volume:59 ; year:2016 ; number:13-14 ; day:10 ; month:06 ; pages:1110-1122 |
Links: |
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DOI / URN: |
10.1007/s11244-016-0630-y |
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Katalog-ID: |
SPR018118496 |
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245 | 1 | 0 | |a Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis |
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520 | |a Abstract The effect of calixarene ligand symmetry, as dictated by lower-rim substitution pattern, on the coordination to a Ti(IV) cation is assessed in solution and when grafted on $ SiO_{2} $, and its effect on epoxidation catalysis by Ti(IV)-calixarene grafted on $ SiO_{2} $ is investigated. $ C_{2v} $ symmetric Ti-tert-butylcalix[4]arene complexes that are 1,3-alkyl disubstituted at the lower rim (di-R-Ti) are compared to previously reported grafted $ C_{s} $ symmetric complexes, which are singly substituted at the lower rim (mono-R-Ti). 13C MAS NMR spectra of complexes isotopically enriched at the lower-rim alkyl position indicate that di-R-Ti predominantly grafts onto silica as the conformation found in solution, exhibiting a deshielded alkyl resonance compared to the grafted mono-R-Ti complexes, which is consistent with stronger alkyl ether→Ti dative interactions that are hypothesized to result in higher electron density at the Ti center. Moreover, 13C MAS NMR spectroscopy detects an additional contribution from an “endo” conformer for grafted di-R-Ti sites, which is not observed in solution. Based on prior molecular modeling studies and on 13C MAS NMR spectroscopy chemical shifts, this “endo” conformer is proposed to have similar Ti–(alkyl ether) distances at the lower-rim and electron density at the Ti center relative to grafted mono-R-Ti complexes. Differences between grafted mono-R-Ti and di-R-Ti sites can be observed by ligand-to-metal charge transfer edge-energies, calculated from diffuse-reflectance UV–visible spectroscopy at 2.24 ± 0.02 and 2.16 ± 0.02 eV, respectively. However, rates of tert-butyl hydroperoxide consumption in the epoxidation of 1-octene are found to be largely unchanged when compared to those of the grafted mono-R-Ti complexes, with average rate constants of ~1.5 $ M^{−2} $ $ s^{−1} $ and initial TOF of ~4 $ ks^{−1} $ at 323 K. This suggests that an “endo” conformation of grafted di-R-Ti may prevail during catalysis. Despite this, grafted di-$ C_{1} $-Ti complexes can be more selective than mono-$ C_{1} $-Ti complexes (45 vs. 34 % at a 50 % conversion at 338 and 353 K), illustrating the importance of the Ti coordination environment on epoxidation catalysis. | ||
650 | 4 | |a Terminal olefin epoxidation |7 (dpeaa)DE-He213 | |
650 | 4 | |a Titanium calixarene |7 (dpeaa)DE-He213 | |
650 | 4 | |a Organic hydroperoxide |7 (dpeaa)DE-He213 | |
650 | 4 | |a Tert-butyl hydroperoxide |7 (dpeaa)DE-He213 | |
650 | 4 | |a Heterogeneous catalysis |7 (dpeaa)DE-He213 | |
650 | 4 | |a Coordination environment |7 (dpeaa)DE-He213 | |
650 | 4 | |a Ligand-to-metal charge-transfer |7 (dpeaa)DE-He213 | |
650 | 4 | |a Grafted organometallic complex conformation |7 (dpeaa)DE-He213 | |
700 | 1 | |a Solovyov, Andrew |e verfasserin |4 aut | |
700 | 1 | |a Hwang, Sonjong |e verfasserin |4 aut | |
700 | 1 | |a Katz, Alexander |e verfasserin |4 aut | |
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773 | 1 | 8 | |g volume:59 |g year:2016 |g number:13-14 |g day:10 |g month:06 |g pages:1110-1122 |
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10.1007/s11244-016-0630-y doi (DE-627)SPR018118496 (SPR)s11244-016-0630-y-e DE-627 ger DE-627 rakwb eng 540 ASE 35.17 bkl Grosso-Giordano, Nicolás A. verfasserin aut Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis 2016 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The effect of calixarene ligand symmetry, as dictated by lower-rim substitution pattern, on the coordination to a Ti(IV) cation is assessed in solution and when grafted on $ SiO_{2} $, and its effect on epoxidation catalysis by Ti(IV)-calixarene grafted on $ SiO_{2} $ is investigated. $ C_{2v} $ symmetric Ti-tert-butylcalix[4]arene complexes that are 1,3-alkyl disubstituted at the lower rim (di-R-Ti) are compared to previously reported grafted $ C_{s} $ symmetric complexes, which are singly substituted at the lower rim (mono-R-Ti). 13C MAS NMR spectra of complexes isotopically enriched at the lower-rim alkyl position indicate that di-R-Ti predominantly grafts onto silica as the conformation found in solution, exhibiting a deshielded alkyl resonance compared to the grafted mono-R-Ti complexes, which is consistent with stronger alkyl ether→Ti dative interactions that are hypothesized to result in higher electron density at the Ti center. Moreover, 13C MAS NMR spectroscopy detects an additional contribution from an “endo” conformer for grafted di-R-Ti sites, which is not observed in solution. Based on prior molecular modeling studies and on 13C MAS NMR spectroscopy chemical shifts, this “endo” conformer is proposed to have similar Ti–(alkyl ether) distances at the lower-rim and electron density at the Ti center relative to grafted mono-R-Ti complexes. Differences between grafted mono-R-Ti and di-R-Ti sites can be observed by ligand-to-metal charge transfer edge-energies, calculated from diffuse-reflectance UV–visible spectroscopy at 2.24 ± 0.02 and 2.16 ± 0.02 eV, respectively. However, rates of tert-butyl hydroperoxide consumption in the epoxidation of 1-octene are found to be largely unchanged when compared to those of the grafted mono-R-Ti complexes, with average rate constants of ~1.5 $ M^{−2} $ $ s^{−1} $ and initial TOF of ~4 $ ks^{−1} $ at 323 K. This suggests that an “endo” conformation of grafted di-R-Ti may prevail during catalysis. Despite this, grafted di-$ C_{1} $-Ti complexes can be more selective than mono-$ C_{1} $-Ti complexes (45 vs. 34 % at a 50 % conversion at 338 and 353 K), illustrating the importance of the Ti coordination environment on epoxidation catalysis. Terminal olefin epoxidation (dpeaa)DE-He213 Titanium calixarene (dpeaa)DE-He213 Organic hydroperoxide (dpeaa)DE-He213 Tert-butyl hydroperoxide (dpeaa)DE-He213 Heterogeneous catalysis (dpeaa)DE-He213 Coordination environment (dpeaa)DE-He213 Ligand-to-metal charge-transfer (dpeaa)DE-He213 Grafted organometallic complex conformation (dpeaa)DE-He213 Solovyov, Andrew verfasserin aut Hwang, Sonjong verfasserin aut Katz, Alexander verfasserin aut Enthalten in Topics in catalysis Bussum : Baltzer, 1994 59(2016), 13-14 vom: 10. Juni, Seite 1110-1122 (DE-627)306712660 (DE-600)1500978-6 1572-9028 nnns volume:59 year:2016 number:13-14 day:10 month:06 pages:1110-1122 https://dx.doi.org/10.1007/s11244-016-0630-y lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-PHA GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_206 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 35.17 ASE AR 59 2016 13-14 10 06 1110-1122 |
spelling |
10.1007/s11244-016-0630-y doi (DE-627)SPR018118496 (SPR)s11244-016-0630-y-e DE-627 ger DE-627 rakwb eng 540 ASE 35.17 bkl Grosso-Giordano, Nicolás A. verfasserin aut Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis 2016 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The effect of calixarene ligand symmetry, as dictated by lower-rim substitution pattern, on the coordination to a Ti(IV) cation is assessed in solution and when grafted on $ SiO_{2} $, and its effect on epoxidation catalysis by Ti(IV)-calixarene grafted on $ SiO_{2} $ is investigated. $ C_{2v} $ symmetric Ti-tert-butylcalix[4]arene complexes that are 1,3-alkyl disubstituted at the lower rim (di-R-Ti) are compared to previously reported grafted $ C_{s} $ symmetric complexes, which are singly substituted at the lower rim (mono-R-Ti). 13C MAS NMR spectra of complexes isotopically enriched at the lower-rim alkyl position indicate that di-R-Ti predominantly grafts onto silica as the conformation found in solution, exhibiting a deshielded alkyl resonance compared to the grafted mono-R-Ti complexes, which is consistent with stronger alkyl ether→Ti dative interactions that are hypothesized to result in higher electron density at the Ti center. Moreover, 13C MAS NMR spectroscopy detects an additional contribution from an “endo” conformer for grafted di-R-Ti sites, which is not observed in solution. Based on prior molecular modeling studies and on 13C MAS NMR spectroscopy chemical shifts, this “endo” conformer is proposed to have similar Ti–(alkyl ether) distances at the lower-rim and electron density at the Ti center relative to grafted mono-R-Ti complexes. Differences between grafted mono-R-Ti and di-R-Ti sites can be observed by ligand-to-metal charge transfer edge-energies, calculated from diffuse-reflectance UV–visible spectroscopy at 2.24 ± 0.02 and 2.16 ± 0.02 eV, respectively. However, rates of tert-butyl hydroperoxide consumption in the epoxidation of 1-octene are found to be largely unchanged when compared to those of the grafted mono-R-Ti complexes, with average rate constants of ~1.5 $ M^{−2} $ $ s^{−1} $ and initial TOF of ~4 $ ks^{−1} $ at 323 K. This suggests that an “endo” conformation of grafted di-R-Ti may prevail during catalysis. Despite this, grafted di-$ C_{1} $-Ti complexes can be more selective than mono-$ C_{1} $-Ti complexes (45 vs. 34 % at a 50 % conversion at 338 and 353 K), illustrating the importance of the Ti coordination environment on epoxidation catalysis. Terminal olefin epoxidation (dpeaa)DE-He213 Titanium calixarene (dpeaa)DE-He213 Organic hydroperoxide (dpeaa)DE-He213 Tert-butyl hydroperoxide (dpeaa)DE-He213 Heterogeneous catalysis (dpeaa)DE-He213 Coordination environment (dpeaa)DE-He213 Ligand-to-metal charge-transfer (dpeaa)DE-He213 Grafted organometallic complex conformation (dpeaa)DE-He213 Solovyov, Andrew verfasserin aut Hwang, Sonjong verfasserin aut Katz, Alexander verfasserin aut Enthalten in Topics in catalysis Bussum : Baltzer, 1994 59(2016), 13-14 vom: 10. Juni, Seite 1110-1122 (DE-627)306712660 (DE-600)1500978-6 1572-9028 nnns volume:59 year:2016 number:13-14 day:10 month:06 pages:1110-1122 https://dx.doi.org/10.1007/s11244-016-0630-y lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-PHA GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_206 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 35.17 ASE AR 59 2016 13-14 10 06 1110-1122 |
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10.1007/s11244-016-0630-y doi (DE-627)SPR018118496 (SPR)s11244-016-0630-y-e DE-627 ger DE-627 rakwb eng 540 ASE 35.17 bkl Grosso-Giordano, Nicolás A. verfasserin aut Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis 2016 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The effect of calixarene ligand symmetry, as dictated by lower-rim substitution pattern, on the coordination to a Ti(IV) cation is assessed in solution and when grafted on $ SiO_{2} $, and its effect on epoxidation catalysis by Ti(IV)-calixarene grafted on $ SiO_{2} $ is investigated. $ C_{2v} $ symmetric Ti-tert-butylcalix[4]arene complexes that are 1,3-alkyl disubstituted at the lower rim (di-R-Ti) are compared to previously reported grafted $ C_{s} $ symmetric complexes, which are singly substituted at the lower rim (mono-R-Ti). 13C MAS NMR spectra of complexes isotopically enriched at the lower-rim alkyl position indicate that di-R-Ti predominantly grafts onto silica as the conformation found in solution, exhibiting a deshielded alkyl resonance compared to the grafted mono-R-Ti complexes, which is consistent with stronger alkyl ether→Ti dative interactions that are hypothesized to result in higher electron density at the Ti center. Moreover, 13C MAS NMR spectroscopy detects an additional contribution from an “endo” conformer for grafted di-R-Ti sites, which is not observed in solution. Based on prior molecular modeling studies and on 13C MAS NMR spectroscopy chemical shifts, this “endo” conformer is proposed to have similar Ti–(alkyl ether) distances at the lower-rim and electron density at the Ti center relative to grafted mono-R-Ti complexes. Differences between grafted mono-R-Ti and di-R-Ti sites can be observed by ligand-to-metal charge transfer edge-energies, calculated from diffuse-reflectance UV–visible spectroscopy at 2.24 ± 0.02 and 2.16 ± 0.02 eV, respectively. However, rates of tert-butyl hydroperoxide consumption in the epoxidation of 1-octene are found to be largely unchanged when compared to those of the grafted mono-R-Ti complexes, with average rate constants of ~1.5 $ M^{−2} $ $ s^{−1} $ and initial TOF of ~4 $ ks^{−1} $ at 323 K. This suggests that an “endo” conformation of grafted di-R-Ti may prevail during catalysis. Despite this, grafted di-$ C_{1} $-Ti complexes can be more selective than mono-$ C_{1} $-Ti complexes (45 vs. 34 % at a 50 % conversion at 338 and 353 K), illustrating the importance of the Ti coordination environment on epoxidation catalysis. Terminal olefin epoxidation (dpeaa)DE-He213 Titanium calixarene (dpeaa)DE-He213 Organic hydroperoxide (dpeaa)DE-He213 Tert-butyl hydroperoxide (dpeaa)DE-He213 Heterogeneous catalysis (dpeaa)DE-He213 Coordination environment (dpeaa)DE-He213 Ligand-to-metal charge-transfer (dpeaa)DE-He213 Grafted organometallic complex conformation (dpeaa)DE-He213 Solovyov, Andrew verfasserin aut Hwang, Sonjong verfasserin aut Katz, Alexander verfasserin aut Enthalten in Topics in catalysis Bussum : Baltzer, 1994 59(2016), 13-14 vom: 10. Juni, Seite 1110-1122 (DE-627)306712660 (DE-600)1500978-6 1572-9028 nnns volume:59 year:2016 number:13-14 day:10 month:06 pages:1110-1122 https://dx.doi.org/10.1007/s11244-016-0630-y lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-PHA GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_206 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 35.17 ASE AR 59 2016 13-14 10 06 1110-1122 |
allfieldsGer |
10.1007/s11244-016-0630-y doi (DE-627)SPR018118496 (SPR)s11244-016-0630-y-e DE-627 ger DE-627 rakwb eng 540 ASE 35.17 bkl Grosso-Giordano, Nicolás A. verfasserin aut Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis 2016 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The effect of calixarene ligand symmetry, as dictated by lower-rim substitution pattern, on the coordination to a Ti(IV) cation is assessed in solution and when grafted on $ SiO_{2} $, and its effect on epoxidation catalysis by Ti(IV)-calixarene grafted on $ SiO_{2} $ is investigated. $ C_{2v} $ symmetric Ti-tert-butylcalix[4]arene complexes that are 1,3-alkyl disubstituted at the lower rim (di-R-Ti) are compared to previously reported grafted $ C_{s} $ symmetric complexes, which are singly substituted at the lower rim (mono-R-Ti). 13C MAS NMR spectra of complexes isotopically enriched at the lower-rim alkyl position indicate that di-R-Ti predominantly grafts onto silica as the conformation found in solution, exhibiting a deshielded alkyl resonance compared to the grafted mono-R-Ti complexes, which is consistent with stronger alkyl ether→Ti dative interactions that are hypothesized to result in higher electron density at the Ti center. Moreover, 13C MAS NMR spectroscopy detects an additional contribution from an “endo” conformer for grafted di-R-Ti sites, which is not observed in solution. Based on prior molecular modeling studies and on 13C MAS NMR spectroscopy chemical shifts, this “endo” conformer is proposed to have similar Ti–(alkyl ether) distances at the lower-rim and electron density at the Ti center relative to grafted mono-R-Ti complexes. Differences between grafted mono-R-Ti and di-R-Ti sites can be observed by ligand-to-metal charge transfer edge-energies, calculated from diffuse-reflectance UV–visible spectroscopy at 2.24 ± 0.02 and 2.16 ± 0.02 eV, respectively. However, rates of tert-butyl hydroperoxide consumption in the epoxidation of 1-octene are found to be largely unchanged when compared to those of the grafted mono-R-Ti complexes, with average rate constants of ~1.5 $ M^{−2} $ $ s^{−1} $ and initial TOF of ~4 $ ks^{−1} $ at 323 K. This suggests that an “endo” conformation of grafted di-R-Ti may prevail during catalysis. Despite this, grafted di-$ C_{1} $-Ti complexes can be more selective than mono-$ C_{1} $-Ti complexes (45 vs. 34 % at a 50 % conversion at 338 and 353 K), illustrating the importance of the Ti coordination environment on epoxidation catalysis. Terminal olefin epoxidation (dpeaa)DE-He213 Titanium calixarene (dpeaa)DE-He213 Organic hydroperoxide (dpeaa)DE-He213 Tert-butyl hydroperoxide (dpeaa)DE-He213 Heterogeneous catalysis (dpeaa)DE-He213 Coordination environment (dpeaa)DE-He213 Ligand-to-metal charge-transfer (dpeaa)DE-He213 Grafted organometallic complex conformation (dpeaa)DE-He213 Solovyov, Andrew verfasserin aut Hwang, Sonjong verfasserin aut Katz, Alexander verfasserin aut Enthalten in Topics in catalysis Bussum : Baltzer, 1994 59(2016), 13-14 vom: 10. Juni, Seite 1110-1122 (DE-627)306712660 (DE-600)1500978-6 1572-9028 nnns volume:59 year:2016 number:13-14 day:10 month:06 pages:1110-1122 https://dx.doi.org/10.1007/s11244-016-0630-y lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-PHA GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_206 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 35.17 ASE AR 59 2016 13-14 10 06 1110-1122 |
allfieldsSound |
10.1007/s11244-016-0630-y doi (DE-627)SPR018118496 (SPR)s11244-016-0630-y-e DE-627 ger DE-627 rakwb eng 540 ASE 35.17 bkl Grosso-Giordano, Nicolás A. verfasserin aut Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis 2016 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The effect of calixarene ligand symmetry, as dictated by lower-rim substitution pattern, on the coordination to a Ti(IV) cation is assessed in solution and when grafted on $ SiO_{2} $, and its effect on epoxidation catalysis by Ti(IV)-calixarene grafted on $ SiO_{2} $ is investigated. $ C_{2v} $ symmetric Ti-tert-butylcalix[4]arene complexes that are 1,3-alkyl disubstituted at the lower rim (di-R-Ti) are compared to previously reported grafted $ C_{s} $ symmetric complexes, which are singly substituted at the lower rim (mono-R-Ti). 13C MAS NMR spectra of complexes isotopically enriched at the lower-rim alkyl position indicate that di-R-Ti predominantly grafts onto silica as the conformation found in solution, exhibiting a deshielded alkyl resonance compared to the grafted mono-R-Ti complexes, which is consistent with stronger alkyl ether→Ti dative interactions that are hypothesized to result in higher electron density at the Ti center. Moreover, 13C MAS NMR spectroscopy detects an additional contribution from an “endo” conformer for grafted di-R-Ti sites, which is not observed in solution. Based on prior molecular modeling studies and on 13C MAS NMR spectroscopy chemical shifts, this “endo” conformer is proposed to have similar Ti–(alkyl ether) distances at the lower-rim and electron density at the Ti center relative to grafted mono-R-Ti complexes. Differences between grafted mono-R-Ti and di-R-Ti sites can be observed by ligand-to-metal charge transfer edge-energies, calculated from diffuse-reflectance UV–visible spectroscopy at 2.24 ± 0.02 and 2.16 ± 0.02 eV, respectively. However, rates of tert-butyl hydroperoxide consumption in the epoxidation of 1-octene are found to be largely unchanged when compared to those of the grafted mono-R-Ti complexes, with average rate constants of ~1.5 $ M^{−2} $ $ s^{−1} $ and initial TOF of ~4 $ ks^{−1} $ at 323 K. This suggests that an “endo” conformation of grafted di-R-Ti may prevail during catalysis. Despite this, grafted di-$ C_{1} $-Ti complexes can be more selective than mono-$ C_{1} $-Ti complexes (45 vs. 34 % at a 50 % conversion at 338 and 353 K), illustrating the importance of the Ti coordination environment on epoxidation catalysis. Terminal olefin epoxidation (dpeaa)DE-He213 Titanium calixarene (dpeaa)DE-He213 Organic hydroperoxide (dpeaa)DE-He213 Tert-butyl hydroperoxide (dpeaa)DE-He213 Heterogeneous catalysis (dpeaa)DE-He213 Coordination environment (dpeaa)DE-He213 Ligand-to-metal charge-transfer (dpeaa)DE-He213 Grafted organometallic complex conformation (dpeaa)DE-He213 Solovyov, Andrew verfasserin aut Hwang, Sonjong verfasserin aut Katz, Alexander verfasserin aut Enthalten in Topics in catalysis Bussum : Baltzer, 1994 59(2016), 13-14 vom: 10. Juni, Seite 1110-1122 (DE-627)306712660 (DE-600)1500978-6 1572-9028 nnns volume:59 year:2016 number:13-14 day:10 month:06 pages:1110-1122 https://dx.doi.org/10.1007/s11244-016-0630-y lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-PHA GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_206 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 35.17 ASE AR 59 2016 13-14 10 06 1110-1122 |
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Enthalten in Topics in catalysis 59(2016), 13-14 vom: 10. Juni, Seite 1110-1122 volume:59 year:2016 number:13-14 day:10 month:06 pages:1110-1122 |
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Terminal olefin epoxidation Titanium calixarene Organic hydroperoxide Tert-butyl hydroperoxide Heterogeneous catalysis Coordination environment Ligand-to-metal charge-transfer Grafted organometallic complex conformation |
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Grosso-Giordano, Nicolás A. @@aut@@ Solovyov, Andrew @@aut@@ Hwang, Sonjong @@aut@@ Katz, Alexander @@aut@@ |
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2016-06-10T00:00:00Z |
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<?xml version="1.0" encoding="UTF-8"?><collection xmlns="http://www.loc.gov/MARC21/slim"><record><leader>01000caa a22002652 4500</leader><controlfield tag="001">SPR018118496</controlfield><controlfield tag="003">DE-627</controlfield><controlfield tag="005">20230519175107.0</controlfield><controlfield tag="007">cr uuu---uuuuu</controlfield><controlfield tag="008">201006s2016 xx |||||o 00| ||eng c</controlfield><datafield tag="024" ind1="7" ind2=" "><subfield code="a">10.1007/s11244-016-0630-y</subfield><subfield code="2">doi</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(DE-627)SPR018118496</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(SPR)s11244-016-0630-y-e</subfield></datafield><datafield tag="040" ind1=" " ind2=" "><subfield code="a">DE-627</subfield><subfield code="b">ger</subfield><subfield code="c">DE-627</subfield><subfield code="e">rakwb</subfield></datafield><datafield tag="041" ind1=" " ind2=" "><subfield code="a">eng</subfield></datafield><datafield tag="082" ind1="0" ind2="4"><subfield code="a">540</subfield><subfield code="q">ASE</subfield></datafield><datafield tag="084" ind1=" " ind2=" "><subfield code="a">35.17</subfield><subfield code="2">bkl</subfield></datafield><datafield tag="100" ind1="1" ind2=" "><subfield code="a">Grosso-Giordano, Nicolás A.</subfield><subfield code="e">verfasserin</subfield><subfield code="4">aut</subfield></datafield><datafield tag="245" ind1="1" ind2="0"><subfield code="a">Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis</subfield></datafield><datafield tag="264" ind1=" " ind2="1"><subfield code="c">2016</subfield></datafield><datafield tag="336" ind1=" " ind2=" "><subfield code="a">Text</subfield><subfield code="b">txt</subfield><subfield code="2">rdacontent</subfield></datafield><datafield tag="337" ind1=" " ind2=" "><subfield code="a">Computermedien</subfield><subfield code="b">c</subfield><subfield code="2">rdamedia</subfield></datafield><datafield tag="338" ind1=" " ind2=" "><subfield code="a">Online-Ressource</subfield><subfield code="b">cr</subfield><subfield code="2">rdacarrier</subfield></datafield><datafield tag="520" ind1=" " ind2=" "><subfield code="a">Abstract The effect of calixarene ligand symmetry, as dictated by lower-rim substitution pattern, on the coordination to a Ti(IV) cation is assessed in solution and when grafted on $ SiO_{2} $, and its effect on epoxidation catalysis by Ti(IV)-calixarene grafted on $ SiO_{2} $ is investigated. $ C_{2v} $ symmetric Ti-tert-butylcalix[4]arene complexes that are 1,3-alkyl disubstituted at the lower rim (di-R-Ti) are compared to previously reported grafted $ C_{s} $ symmetric complexes, which are singly substituted at the lower rim (mono-R-Ti). 13C MAS NMR spectra of complexes isotopically enriched at the lower-rim alkyl position indicate that di-R-Ti predominantly grafts onto silica as the conformation found in solution, exhibiting a deshielded alkyl resonance compared to the grafted mono-R-Ti complexes, which is consistent with stronger alkyl ether→Ti dative interactions that are hypothesized to result in higher electron density at the Ti center. Moreover, 13C MAS NMR spectroscopy detects an additional contribution from an “endo” conformer for grafted di-R-Ti sites, which is not observed in solution. Based on prior molecular modeling studies and on 13C MAS NMR spectroscopy chemical shifts, this “endo” conformer is proposed to have similar Ti–(alkyl ether) distances at the lower-rim and electron density at the Ti center relative to grafted mono-R-Ti complexes. Differences between grafted mono-R-Ti and di-R-Ti sites can be observed by ligand-to-metal charge transfer edge-energies, calculated from diffuse-reflectance UV–visible spectroscopy at 2.24 ± 0.02 and 2.16 ± 0.02 eV, respectively. However, rates of tert-butyl hydroperoxide consumption in the epoxidation of 1-octene are found to be largely unchanged when compared to those of the grafted mono-R-Ti complexes, with average rate constants of ~1.5 $ M^{−2} $ $ s^{−1} $ and initial TOF of ~4 $ ks^{−1} $ at 323 K. This suggests that an “endo” conformation of grafted di-R-Ti may prevail during catalysis. Despite this, grafted di-$ C_{1} $-Ti complexes can be more selective than mono-$ C_{1} $-Ti complexes (45 vs. 34 % at a 50 % conversion at 338 and 353 K), illustrating the importance of the Ti coordination environment on epoxidation catalysis.</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Terminal olefin epoxidation</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Titanium calixarene</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Organic hydroperoxide</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Tert-butyl hydroperoxide</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Heterogeneous catalysis</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Coordination environment</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Ligand-to-metal charge-transfer</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Grafted organometallic complex conformation</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="700" ind1="1" ind2=" "><subfield code="a">Solovyov, Andrew</subfield><subfield code="e">verfasserin</subfield><subfield code="4">aut</subfield></datafield><datafield tag="700" ind1="1" ind2=" "><subfield code="a">Hwang, Sonjong</subfield><subfield code="e">verfasserin</subfield><subfield code="4">aut</subfield></datafield><datafield tag="700" ind1="1" ind2=" "><subfield code="a">Katz, Alexander</subfield><subfield code="e">verfasserin</subfield><subfield code="4">aut</subfield></datafield><datafield tag="773" ind1="0" ind2="8"><subfield code="i">Enthalten in</subfield><subfield code="t">Topics in catalysis</subfield><subfield code="d">Bussum : Baltzer, 1994</subfield><subfield code="g">59(2016), 13-14 vom: 10. 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|
author |
Grosso-Giordano, Nicolás A. |
spellingShingle |
Grosso-Giordano, Nicolás A. ddc 540 bkl 35.17 misc Terminal olefin epoxidation misc Titanium calixarene misc Organic hydroperoxide misc Tert-butyl hydroperoxide misc Heterogeneous catalysis misc Coordination environment misc Ligand-to-metal charge-transfer misc Grafted organometallic complex conformation Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis |
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Grosso-Giordano, Nicolás A. |
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540 - Chemistry & allied sciences |
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1572-9028 |
topic_title |
540 ASE 35.17 bkl Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis Terminal olefin epoxidation (dpeaa)DE-He213 Titanium calixarene (dpeaa)DE-He213 Organic hydroperoxide (dpeaa)DE-He213 Tert-butyl hydroperoxide (dpeaa)DE-He213 Heterogeneous catalysis (dpeaa)DE-He213 Coordination environment (dpeaa)DE-He213 Ligand-to-metal charge-transfer (dpeaa)DE-He213 Grafted organometallic complex conformation (dpeaa)DE-He213 |
topic |
ddc 540 bkl 35.17 misc Terminal olefin epoxidation misc Titanium calixarene misc Organic hydroperoxide misc Tert-butyl hydroperoxide misc Heterogeneous catalysis misc Coordination environment misc Ligand-to-metal charge-transfer misc Grafted organometallic complex conformation |
topic_unstemmed |
ddc 540 bkl 35.17 misc Terminal olefin epoxidation misc Titanium calixarene misc Organic hydroperoxide misc Tert-butyl hydroperoxide misc Heterogeneous catalysis misc Coordination environment misc Ligand-to-metal charge-transfer misc Grafted organometallic complex conformation |
topic_browse |
ddc 540 bkl 35.17 misc Terminal olefin epoxidation misc Titanium calixarene misc Organic hydroperoxide misc Tert-butyl hydroperoxide misc Heterogeneous catalysis misc Coordination environment misc Ligand-to-metal charge-transfer misc Grafted organometallic complex conformation |
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Elektronische Aufsätze Aufsätze Elektronische Ressource |
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Topics in catalysis |
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306712660 |
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540 - Chemistry |
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Topics in catalysis |
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Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis |
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title_full |
Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis |
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Grosso-Giordano, Nicolás A. |
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Topics in catalysis |
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Grosso-Giordano, Nicolás A. Solovyov, Andrew Hwang, Sonjong Katz, Alexander |
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Elektronische Aufsätze |
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Grosso-Giordano, Nicolás A. |
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10.1007/s11244-016-0630-y |
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title_sort |
effect of coordination environment in grafted single-site ti-$ sio_{2} $ olefin epoxidation catalysis |
title_auth |
Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis |
abstract |
Abstract The effect of calixarene ligand symmetry, as dictated by lower-rim substitution pattern, on the coordination to a Ti(IV) cation is assessed in solution and when grafted on $ SiO_{2} $, and its effect on epoxidation catalysis by Ti(IV)-calixarene grafted on $ SiO_{2} $ is investigated. $ C_{2v} $ symmetric Ti-tert-butylcalix[4]arene complexes that are 1,3-alkyl disubstituted at the lower rim (di-R-Ti) are compared to previously reported grafted $ C_{s} $ symmetric complexes, which are singly substituted at the lower rim (mono-R-Ti). 13C MAS NMR spectra of complexes isotopically enriched at the lower-rim alkyl position indicate that di-R-Ti predominantly grafts onto silica as the conformation found in solution, exhibiting a deshielded alkyl resonance compared to the grafted mono-R-Ti complexes, which is consistent with stronger alkyl ether→Ti dative interactions that are hypothesized to result in higher electron density at the Ti center. Moreover, 13C MAS NMR spectroscopy detects an additional contribution from an “endo” conformer for grafted di-R-Ti sites, which is not observed in solution. Based on prior molecular modeling studies and on 13C MAS NMR spectroscopy chemical shifts, this “endo” conformer is proposed to have similar Ti–(alkyl ether) distances at the lower-rim and electron density at the Ti center relative to grafted mono-R-Ti complexes. Differences between grafted mono-R-Ti and di-R-Ti sites can be observed by ligand-to-metal charge transfer edge-energies, calculated from diffuse-reflectance UV–visible spectroscopy at 2.24 ± 0.02 and 2.16 ± 0.02 eV, respectively. However, rates of tert-butyl hydroperoxide consumption in the epoxidation of 1-octene are found to be largely unchanged when compared to those of the grafted mono-R-Ti complexes, with average rate constants of ~1.5 $ M^{−2} $ $ s^{−1} $ and initial TOF of ~4 $ ks^{−1} $ at 323 K. This suggests that an “endo” conformation of grafted di-R-Ti may prevail during catalysis. Despite this, grafted di-$ C_{1} $-Ti complexes can be more selective than mono-$ C_{1} $-Ti complexes (45 vs. 34 % at a 50 % conversion at 338 and 353 K), illustrating the importance of the Ti coordination environment on epoxidation catalysis. |
abstractGer |
Abstract The effect of calixarene ligand symmetry, as dictated by lower-rim substitution pattern, on the coordination to a Ti(IV) cation is assessed in solution and when grafted on $ SiO_{2} $, and its effect on epoxidation catalysis by Ti(IV)-calixarene grafted on $ SiO_{2} $ is investigated. $ C_{2v} $ symmetric Ti-tert-butylcalix[4]arene complexes that are 1,3-alkyl disubstituted at the lower rim (di-R-Ti) are compared to previously reported grafted $ C_{s} $ symmetric complexes, which are singly substituted at the lower rim (mono-R-Ti). 13C MAS NMR spectra of complexes isotopically enriched at the lower-rim alkyl position indicate that di-R-Ti predominantly grafts onto silica as the conformation found in solution, exhibiting a deshielded alkyl resonance compared to the grafted mono-R-Ti complexes, which is consistent with stronger alkyl ether→Ti dative interactions that are hypothesized to result in higher electron density at the Ti center. Moreover, 13C MAS NMR spectroscopy detects an additional contribution from an “endo” conformer for grafted di-R-Ti sites, which is not observed in solution. Based on prior molecular modeling studies and on 13C MAS NMR spectroscopy chemical shifts, this “endo” conformer is proposed to have similar Ti–(alkyl ether) distances at the lower-rim and electron density at the Ti center relative to grafted mono-R-Ti complexes. Differences between grafted mono-R-Ti and di-R-Ti sites can be observed by ligand-to-metal charge transfer edge-energies, calculated from diffuse-reflectance UV–visible spectroscopy at 2.24 ± 0.02 and 2.16 ± 0.02 eV, respectively. However, rates of tert-butyl hydroperoxide consumption in the epoxidation of 1-octene are found to be largely unchanged when compared to those of the grafted mono-R-Ti complexes, with average rate constants of ~1.5 $ M^{−2} $ $ s^{−1} $ and initial TOF of ~4 $ ks^{−1} $ at 323 K. This suggests that an “endo” conformation of grafted di-R-Ti may prevail during catalysis. Despite this, grafted di-$ C_{1} $-Ti complexes can be more selective than mono-$ C_{1} $-Ti complexes (45 vs. 34 % at a 50 % conversion at 338 and 353 K), illustrating the importance of the Ti coordination environment on epoxidation catalysis. |
abstract_unstemmed |
Abstract The effect of calixarene ligand symmetry, as dictated by lower-rim substitution pattern, on the coordination to a Ti(IV) cation is assessed in solution and when grafted on $ SiO_{2} $, and its effect on epoxidation catalysis by Ti(IV)-calixarene grafted on $ SiO_{2} $ is investigated. $ C_{2v} $ symmetric Ti-tert-butylcalix[4]arene complexes that are 1,3-alkyl disubstituted at the lower rim (di-R-Ti) are compared to previously reported grafted $ C_{s} $ symmetric complexes, which are singly substituted at the lower rim (mono-R-Ti). 13C MAS NMR spectra of complexes isotopically enriched at the lower-rim alkyl position indicate that di-R-Ti predominantly grafts onto silica as the conformation found in solution, exhibiting a deshielded alkyl resonance compared to the grafted mono-R-Ti complexes, which is consistent with stronger alkyl ether→Ti dative interactions that are hypothesized to result in higher electron density at the Ti center. Moreover, 13C MAS NMR spectroscopy detects an additional contribution from an “endo” conformer for grafted di-R-Ti sites, which is not observed in solution. Based on prior molecular modeling studies and on 13C MAS NMR spectroscopy chemical shifts, this “endo” conformer is proposed to have similar Ti–(alkyl ether) distances at the lower-rim and electron density at the Ti center relative to grafted mono-R-Ti complexes. Differences between grafted mono-R-Ti and di-R-Ti sites can be observed by ligand-to-metal charge transfer edge-energies, calculated from diffuse-reflectance UV–visible spectroscopy at 2.24 ± 0.02 and 2.16 ± 0.02 eV, respectively. However, rates of tert-butyl hydroperoxide consumption in the epoxidation of 1-octene are found to be largely unchanged when compared to those of the grafted mono-R-Ti complexes, with average rate constants of ~1.5 $ M^{−2} $ $ s^{−1} $ and initial TOF of ~4 $ ks^{−1} $ at 323 K. This suggests that an “endo” conformation of grafted di-R-Ti may prevail during catalysis. Despite this, grafted di-$ C_{1} $-Ti complexes can be more selective than mono-$ C_{1} $-Ti complexes (45 vs. 34 % at a 50 % conversion at 338 and 353 K), illustrating the importance of the Ti coordination environment on epoxidation catalysis. |
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title_short |
Effect of Coordination Environment in Grafted Single-Site Ti-$ SiO_{2} $ Olefin Epoxidation Catalysis |
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score |
7.4009924 |