Skip to main content

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

Topics in Catalysis volume 59, pages 1110–1122 (2016)Cite this article

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 SiO2, and its effect on epoxidation catalysis by Ti(IV)-calixarene grafted on SiO2 is investigated. C2v 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 Cs 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-C1-Ti complexes can be more selective than mono-C1-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.

This is a preview of subscription content, access via your institution.

Access options

Buy single article

Instant access to the full article PDF.

USD 39.95

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

References

  1. Bell AT (2003) The impact of nanoscience on heterogeneous catalysis. Science 299:1688–1691. doi:10.1126/science.1083671

    CAS  Article  Google Scholar 

  2. Copéret C, Chabanas M, Petroff Saint-Arroman R, Basset J-M (2003) Homogeneous and heterogeneous catalysis: bridging the gap through surface organometallic chemistry. Angew Chem Int Ed Engl 42:156–181. doi:10.1002/anie.200390072

    Article  Google Scholar 

  3. Corma A, García H (2002) Lewis acids as catalysts in oxidation reactions: from homogeneous to heterogeneous systems. Chem Rev 102:3837–3892. doi:10.1021/cr010333u

    CAS  Article  Google Scholar 

  4. Corma A (2004) Attempts to fill the gap between enzymatic, homogeneous, and heterogeneous catalysis. Catal Rev 46:369–417. doi:10.1081/CR-200036732

    CAS  Article  Google Scholar 

  5. Dusi M, Mallat T, Baiker A (2000) Epoxidation of functionalized olefins over solid catalysts. Catal Rev 42:213–278. doi:10.1081/CR-100100262

    CAS  Article  Google Scholar 

  6. Marchese L, Gianotti E, Dellarocca V et al (1999) Structure–functionality relationships of grafted Ti-MCM41 silicas. spectroscopic and catalytic studies. Phys Chem Chem Phys 1:585–592. doi:10.1039/a808225a

    CAS  Article  Google Scholar 

  7. Thomas JM, Sankar G (2001) The role of synchrotron-based studies in the elucidation and design of active sites in titanium—silica epoxidation catalysts. Acc Chem Res 34:571–581. doi:10.1021/ar010003w

    CAS  Article  Google Scholar 

  8. Corma A (2003) State of the art and future challenges of zeolites as catalysts. J Catal 216:298–312. doi:10.1016/S0021-9517(02)00132-X

    CAS  Article  Google Scholar 

  9. Saxton RJ (1999) Crystalline microporous titanium silicates. Top Catal 9:43–57. doi:10.1023/A:1019102320274

    CAS  Article  Google Scholar 

  10. Clerici M (1993) Epoxidation of lower olefins with hydrogen peroxide and titanium silicalite. J Catal 140:71–83. doi:10.1006/jcat.1993.1069

    CAS  Article  Google Scholar 

  11. Maschmeyer T, Rey F, Sankar G, Thomas JM (1995) Heterogeneous catalysts obtained by grafting metallocene complexes onto mesoporous silica. Nature 378:159–162. doi:10.1038/378159a0

    CAS  Article  Google Scholar 

  12. Guidotti M, Ravasio N, Psaro R et al (2003) Epoxidation on titanium-containing silicates: do structural features really affect the catalytic performance? J Catal 214:242–250. doi:10.1016/S0021-9517(02)00152-5

    CAS  Article  Google Scholar 

  13. Jarupatrakorn J, Tilley TD (2002) Silica-supported, single-site titanium catalysts for olefin epoxidation. A molecular precursor strategy for control of catalyst structure. J Am Chem Soc 124:8380–8388. doi:10.1021/ja0202208

    CAS  Article  Google Scholar 

  14. Bouh AO, Rice GL, Scott SL (1999) Mono- and dinuclear silica-supported titanium(IV) complexes and the effect of TioTi connectivity on reactivity. J Am Chem Soc 121:7201–7210. doi:10.1021/ja9829160

    CAS  Article  Google Scholar 

  15. Notestein JM, Iglesia E, Katz A (2004) Grafted metallocalixarenes as single-site surface organometallic catalysts. J Am Chem Soc 126:16478–16486. doi:10.1021/ja0470259

    CAS  Article  Google Scholar 

  16. Notestein JM, Solovyov A, Andrini LR et al (2007) The role of outer-sphere surface acidity in alkene epoxidation catalyzed by calixarene-Ti(IV) complexes. J Am Chem Soc 129:15585–15595. doi:10.1021/ja074614g

    CAS  Article  Google Scholar 

  17. Notestein JM, Andrini LR, Kalchenko VI et al (2007) Structural assessment and catalytic consequences of the oxygen coordination environment in grafted Ti-calixarenes. J Am Chem Soc 129:1122–1131. doi:10.1021/ja065830c

    CAS  Article  Google Scholar 

  18. Nandi P, Tang W, Okrut A et al (2013) Catalytic consequences of open and closed grafted Al(III)-calix[4]arene complexes for hydride and oxo transfer reactions. Proc Natl Acad Sci USA 110:2484–2489. doi:10.1073/pnas.1211158110

    CAS  Article  Google Scholar 

  19. Nandi P, Solovyov A, Okrut A, Katz A (2014) Al III–Calix[4]arene catalysts for asymmetric meerwein–ponndorf–verley reduction. ACS Catal 4:2492–2495. doi:10.1021/cs5001976

    CAS  Article  Google Scholar 

  20. de Silva N, Hwang S-J, Durkin KA, Katz A (2009) Vanadocalixarenes on silica: requirements for permanent anchoring and electronic communication. Chem Mater 21:1852–1860. doi:10.1021/cm803392m

    Article  Google Scholar 

  21. Trent DL (2000) Propylene oxide. In: Kirk-Othmer encyclopedia of chemical technology. Wiley, Hoboken

  22. Friedrich A, Radius U (2004) A calix[4]arene monoalkyl ether as a model of a tris(phenolate) ligand with a hemilabile anisole moiety: syntheses, molecular structures and bonding of calix[4]arene ether supported titanium complexes and their catalytic activity in epoxidation reactions. Eur J Inorg Chem 2004:4300–4316. doi:10.1002/ejic.200400430

    Article  Google Scholar 

  23. Zanotti-Gerosa A, Solari E, Giannini L et al (1998) Titanium-carbon functionalities on an oxo surface defined by a calix[4] arene moiety and its redox chemistry. Inorganica Chim Acta 270:298–311. doi:10.1016/S0020-1693(97)05863-5

    CAS  Article  Google Scholar 

  24. Radius U (2001) Shaping the cavity of the macrocyclic ligand in metallocalix[4]arenes: the role of the ligand sphere. Inorg Chem 40:6637–6642. doi:10.1021/ic010482v

    CAS  Article  Google Scholar 

  25. Böhmer V (1995) Calixarene—makrocyclen mit (fast) unbegrenzten möglichkeiten. Angew Chemie 107:785–818. doi:10.1002/ange.19951070704

    Article  Google Scholar 

  26. Dijkstra PJ, Brunink JAJ, Bugge KE et al (1989) Kinetically stable complexes of alkali cations with rigidified calix[4]arenes: synthesis, X-ray structures, and complexation of calixcrowns and calixspherands. J Am Chem Soc 111:7567–7575. doi:10.1021/ja00201a045

    CAS  Article  Google Scholar 

  27. Shang S, Khasnis DV, Burton JM et al (1994) From a novel silyl p-tert-Butylcalix[4]arene triether to mono-O-alkyl substitution: a unique, efficient, and selective route to mono-O-substituted calix[4]arenes. Organometallics 13:5157–5159. doi:10.1021/om00024a067

    CAS  Article  Google Scholar 

  28. Groenen LC, Ruël BHM, Casnati A et al (1991) Synthesis of monoalkylated calix[4]arenes via direct alkylation. Tetrahedron 47:8379–8384. doi:10.1016/S0040-4020(01)96179-4

    CAS  Article  Google Scholar 

  29. van Loon J-D, Verboom W, Reinhoudt DN (1992) Selective functionalization and conformational properties of calix[4]arenes, a review. Org Prep Proced Int 24:437–462. doi:10.1080/00304949209356227

    Article  Google Scholar 

  30. Zawadiak J, Gilner D, Kulicki Z, Baj S (1993) Concurrent iodimetric determination of cumene hydroperoxide and dicumenyl peroxide used for reaction control in dicumenyl peroxide synthesis. Analyst 118:1081. doi:10.1039/an9931801081

    CAS  Article  Google Scholar 

  31. Winner L, Daniloff G, Nichiporuk RV et al (2015) Patterned grafted lewis-acid sites on surfaces: olefin epoxidation catalysis using tetrameric Ti(IV)–calix[4]arene complexes. Top Catal 58:441–450. doi:10.1007/s11244-015-0385-x

    CAS  Article  Google Scholar 

  32. Zhuravlev LT (1987) Concentration of hydroxyl groups on the surface of amorphous silicas. Langmuir 3:316–318. doi:10.1021/la00075a004

    CAS  Article  Google Scholar 

  33. Marchese L, Maschmeyer T, Gianotti E et al (1997) probing the titanium sites in Ti–MCM41 by diffuse reflectance and photoluminescence UV–Vis spectroscopies. J Phys Chem B 101:8836–8838. doi:10.1021/jp971963w

    CAS  Article  Google Scholar 

  34. Notestein JM, Iglesia E, Katz A (2007) Photoluminescence and charge-transfer complexes of calixarenes grafted on TiO 2 nanoparticles. Chem Mater 19:4998–5005. doi:10.1021/cm070779c

    CAS  Article  Google Scholar 

  35. Fantacci S, Sgamellotti A, Re N, Floriani C (2001) Density functional study of tetraphenolate and calix[4]arene complexes of early transition metals. Inorg Chem 40:1544–1549. doi:10.1021/ic0004028

    CAS  Article  Google Scholar 

  36. Prieto-Centurion D, Notestein JM (2011) Surface speciation and alkane oxidation with highly dispersed Fe(III) sites on silica. J Catal 279:103–110. doi:10.1016/j.jcat.2011.01.007

    CAS  Article  Google Scholar 

  37. Böhmer V (1995) Calixarenes, macrocycles with(almost) unlimited possibilities. Angew Chemie 34:785–818. doi:10.1002/anie.199507131

    Article  Google Scholar 

Download references

Acknowledgments

The authors are grateful to Prof. Dr. Udo Radius for providing structural data from previous molecular modeling studies [24] of Ti-calixarene complexes, and Dr. Kathleen Durkin for assistance with data analysis. Funding from the U.S. Department of Energy Office of Basic Energy Sciences (DE-FG02-05ER15696) and the National Science Foundation (IIP 1542974) is gratefully acknowledged.

Author information

Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of California at Berkeley, Berkeley, CA, 94720, USA

    Nicolás A. Grosso-Giordano, Andrew Solovyov & Alexander Katz

  2. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, 91125, USA

    Sonjong Hwang

Authors
  1. Nicolás A. Grosso-Giordano
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Andrew Solovyov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Sonjong Hwang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Alexander Katz
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Alexander Katz.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 3,429 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Grosso-Giordano, N.A., Solovyov, A., Hwang, S. et al. Effect of Coordination Environment in Grafted Single-Site Ti-SiO2 Olefin Epoxidation Catalysis. Top Catal 59, 1110–1122 (2016). https://doi.org/10.1007/s11244-016-0630-y

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11244-016-0630-y

Keywords

  • Terminal olefin epoxidation
  • Titanium calixarene
  • Organic hydroperoxide
  • Tert-butyl hydroperoxide
  • Heterogeneous catalysis
  • Coordination environment
  • Ligand-to-metal charge-transfer
  • Grafted organometallic complex conformation