Structural assessment and catalytic consequences of the oxygen coordination environment in grafted Ti-calixarenes

Justin M Notestein, Leandro R. Andrini, Vitaly I. Kalchenko, Felix G. Requejo, Alexander Katz, Enrique Iglesia

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Abstract

Calixarene-Ti complexes were grafted onto SiO2 (0.18-0.24 Ti nm-2) to form isolated and accessible Ti centers persistently coordinated to multidentate calixarene ligands. Grafted Ti-tert-butylcalix[4] arenes gave Ti K-edge absorption spectra with pre-edge features at 4968.6-4968.9 eV, independently of Ti surface density and of their use in epoxidation catalysis. The structure and reactivity of grafted Ti-calix[4]arenes were weakly dependent on thermal treatment below 573 K, and the relative epoxidation rates of trans- and cis-alkenes showed that calixarene ligands did not restrict access to Ti centers more than corresponding calcined Ti-SiO2 materials. For all materials, 13C NMR and UV-visible spectroscopies confirmed the presence of Ti-O-Si connectivity and identical ligand-to-metal transitions. Grafted Ti-homooxacalix[3]arene complexes, however, gave weaker pre-edge features at higher energies (∼4969.5 eV), consistent with greater Ti 3d occupancy and coordination numbers greater than four, and 20-fold lower cyclohexene epoxidation rate constants (per Ti) than on calix[4]arene-based materials. These different rates and near-edge spectra result from aldehyde formation caused by unimolecular cleavage of ether linkages in homooxacalix[3]arene ligands during grafting, leading to higher coordination and electron density at Ti centers. Materials based on tert-butylcalix[4]arene and homooxacalix[3]arenes led to similar epoxidation rates and near-edge spectra after calcination, consistent with the conversion of both materials to isolated Ti centers with identical structure. These materials provide a systematic approach for relating oxidation reactivity to Ti 3d occupancy, a descriptor of Lewis acid strength, and Ti coordination, because they provide Ti centers with varying electron density and coordination, but maintain accessible active centers with uniform structure and unrestricted access to reactants.

Original languageEnglish
Pages (from-to)1122-1131
Number of pages10
JournalJournal of the American Chemical Society
Volume129
Issue number5
DOIs
Publication statusPublished - Feb 7 2007

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Calixarenes
Epoxidation
Oxygen
Ligands
Electrons
Lewis Acids
Carrier concentration
Alkenes
Catalysis
Aldehydes
Ether
Spectrum Analysis
Hot Temperature
Metals
Calcination
Olefins
Transition metals
Absorption spectra
Ethers
Rate constants

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Structural assessment and catalytic consequences of the oxygen coordination environment in grafted Ti-calixarenes. / Notestein, Justin M; Andrini, Leandro R.; Kalchenko, Vitaly I.; Requejo, Felix G.; Katz, Alexander; Iglesia, Enrique.

In: Journal of the American Chemical Society, Vol. 129, No. 5, 07.02.2007, p. 1122-1131.

Research output: Contribution to journalArticle

Notestein, Justin M ; Andrini, Leandro R. ; Kalchenko, Vitaly I. ; Requejo, Felix G. ; Katz, Alexander ; Iglesia, Enrique. / Structural assessment and catalytic consequences of the oxygen coordination environment in grafted Ti-calixarenes. In: Journal of the American Chemical Society. 2007 ; Vol. 129, No. 5. pp. 1122-1131.
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AB - Calixarene-Ti complexes were grafted onto SiO2 (0.18-0.24 Ti nm-2) to form isolated and accessible Ti centers persistently coordinated to multidentate calixarene ligands. Grafted Ti-tert-butylcalix[4] arenes gave Ti K-edge absorption spectra with pre-edge features at 4968.6-4968.9 eV, independently of Ti surface density and of their use in epoxidation catalysis. The structure and reactivity of grafted Ti-calix[4]arenes were weakly dependent on thermal treatment below 573 K, and the relative epoxidation rates of trans- and cis-alkenes showed that calixarene ligands did not restrict access to Ti centers more than corresponding calcined Ti-SiO2 materials. For all materials, 13C NMR and UV-visible spectroscopies confirmed the presence of Ti-O-Si connectivity and identical ligand-to-metal transitions. Grafted Ti-homooxacalix[3]arene complexes, however, gave weaker pre-edge features at higher energies (∼4969.5 eV), consistent with greater Ti 3d occupancy and coordination numbers greater than four, and 20-fold lower cyclohexene epoxidation rate constants (per Ti) than on calix[4]arene-based materials. These different rates and near-edge spectra result from aldehyde formation caused by unimolecular cleavage of ether linkages in homooxacalix[3]arene ligands during grafting, leading to higher coordination and electron density at Ti centers. Materials based on tert-butylcalix[4]arene and homooxacalix[3]arenes led to similar epoxidation rates and near-edge spectra after calcination, consistent with the conversion of both materials to isolated Ti centers with identical structure. These materials provide a systematic approach for relating oxidation reactivity to Ti 3d occupancy, a descriptor of Lewis acid strength, and Ti coordination, because they provide Ti centers with varying electron density and coordination, but maintain accessible active centers with uniform structure and unrestricted access to reactants.

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