Effect of Coordination Environment in Grafted Single-Site Ti-SiO2 Olefin Epoxidation Catalysis

• Published in: Topics in catalysis Vol. 59; no. 13-14; pp. 1110 - 1122
• Main Authors: Grosso-Giordano, Nicolás A., Solovyov, Andrew, Hwang, Sonjong, Katz, Alexander
• Format: Journal Article
• Language: English
• Published: New York Springer US 01.08.2016
• Subjects: Catalysis; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Industrial Chemistry/Chemical Engineering; Original Paper; Pharmacy; Physical Chemistry; Heterogeneous catalysis; Titanium calixarene; Coordination environment; Organic hydroperoxide; Tert-butyl hydroperoxide; Terminal olefin epoxidation; Ligand-to-metal charge-transfer; Grafted organometallic complex conformation
• ISSN: 1022-5528; 1572-9028
• DOI: 10.1007/s11244-016-0630-y

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). 13 C 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, 13 C 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 13 C 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.