Abstract
A variety of organomolybdenum and organorhenium complexes, most prominently methyltrioxorhenium(VII) (MTO), are applicable as efficient and selective oxidising agents in the presence of organic hydroperoxides (molybdenum complexes) or hydrogen peroxide (rhenium complexes). Besides strictly homogeneous oxidation catalysis, there is increasing interest in immobilizing homogeneous catalysts, both on carrier materials and in ionic liquids. Several methods that differ mainly in the anchoring mode and the nature of the supporting material have been described, and the resulting materials were applied to oxidation catalysis. Chiral oxidation catalysis with the compounds mentioned in the title is still in its infancy, but initial results point towards a promising future. The supported catalysts combine properties of homogeneous catalysts (reactivity, control and selectivity) and heterogeneous catalysts (enhanced stability and reusability). Homogeneous catalysts have a clearly defined composition, and mechanistic examinations are usually less problematic than with bulk (heterogeneous) catalysts, where the active sites are less clearly defined. It is also more straightforward to modify homogeneous catalysts by fine-tuning their ligand environments.
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsPreview
Unable to display preview. Download preview PDF.
Abbreviations
- acac:
-
acetylacetonate
- bpy:
-
2,2′-bipyridyl
- Cp:
-
cyclopentadiene
- dppa:
-
bis(diphenylphosphino)amine
- Et:
-
ethyl
- EXAFS:
-
extended X-ray absorption fine structure
- IR:
-
infrared
- MCM:
-
mobile crystalline material
- Me:
-
methyl
- MTO:
-
methyltrioxorhenium
- NMR:
-
nuclear magnetic resonance
- PBI:
-
polybenzimidazole
- PEO:
-
polyethylene oxide
- Ph:
-
phenyl
- PPO:
-
polypropylene oxide
- PS:
-
polystyrene
- PSHPAMP:
-
polystyrene–divinylbenzene resin carrying an N-(2-hydroxypropyl)- 2-aminomethylpyridine ligand
- PVP:
-
poly(4-vinylpyridine)
- PVPN:
-
poly(4-vinylpyridine-N-oxide)
- RT:
-
room temperature
- RTIL:
-
room temperature ionic liquid
- TBHP:
-
tert-butyl hydroperoxide
- UHP:
-
urea hydroperoxide
References
Kumar SB, Chaudhury M (1991) J Chem Soc Dalton Trans p 2169
Palanca P, Picher T, Sanz V, Gomez-Romero P, Llopis E, Domenech A, Cervilla A (1990) J Chem Soc Chem Commun p 531
Wilshire JP, Leon L, Bosserman P, Sawyer DT (1979) J Am Chem Soc 101:3379
Berg JM, Holm RH (1985) J Am Chem Soc 107:925
Caradonna JP, Harlan EW, Holm RH (1986) J Am Chem Soc 108:7856
Fehrer FJ, Rahimian K, Budzichowski TA, Ziller JW (1995) Organometallics 14:3920
Clarke R, Gahagan M, Mackie RK, Foster DF, Cole-Hamilton DJ, Nicol M, Montford AW (1995) J Chem Soc Dalton Trans p 1221
Backhouse JR, Lowe HM, Sinn E, Suzuki S, Woodward S (1995) J Chem Soc Dalton Trans p 3329
Kollar J (Halcon International Inc.) (1967) US Patent 3 350 422
Kollar J (Halcon International Inc.) (1967) US Patent 3 351 635
Sheng MN, Zajaczek GJ (ARCO) (1968) UK Patent: GB 1 136 923
Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck S (1992) Nature 359:710
Beck S, Vartuli JC, Roth WJ, Leonowicz ME, Kresge CT, Schmitt KD, Chu CT-W, Olson DH, Sheppard EW, McCullen SB, Higgins JB, Schlenker JL (1992) J Am Chem Soc 114:10834
Alfredsson V, Anderson M (1996) Chem Mater 8:1141
Ferreira P, Gonçalves IS, Kühn FE, Lopez AD, Martins MA, Pillinger M, Pina A, Rocha J, Romão CC, Santos AM, Santos TM, Valente AA (2000) Eur J Inorg Chem p 2263
Sakthivel A, Zhao J, Kühn FE (2005) Catal Lett 102:115
Sakthivel A, Zhao J, Hanzlik M, Kühn FE (2004) Dalton Trans p 3338
Corma A, Fuerte A, Iglesias M, Sanchez F (1996) J Mol Catal A–Chem 107:225
Sakthivel A, Zhao J, Hanzlik M, Chiang AST, Herrmann WA, Kühn FE (2005) Adv Synth Catal 347:473
Abrantes M, Gago S, Valente AA, Pillinger M, Gonçalves IS, Santos TM, Rocha J, Romão CC (2004) Eur J Inorg Chem 4914
Sakthivel A, Abrantes M, Chiang AST, Kühn FE (2006) J Organomet Chem 691:1007
Jia M, Thiel WR (2002) Chem Commun p 2392
Jia M, Seifert A, Thiel WR (2003) Chem Mater 15:2174
Nunes CD, Valente AA, Pillinger M, Fernandes AC, Romão CC, Rocha J, Gonçalves IS (2002) J Mater Chem 12:1735
Sakthivel A, Zhao J, Raudaschl-Sieber G, Kühn FE (2005) J Organomet Chem 690:5105
Gonçalves IS, Santos AM, Romão CC, Lopez AD, Rodriguez-Borges JE, Pillinger M, Ferreira P, Rocha J, Kühn FE (2001) J Organomet Chem 626:1
Sakthivel A, Zhao J, Raudaschl-Sieber G, Hanzlik M, Chiang AST, Kühn FE (2005) Appl Cat A 281:267
Jia M, Seifert A, Berger M, Giegengack H, Schulze S, Thiel WR (2004) Chem Mater 16:877
Jia M, Seifert A, Thiel WR (2004) J Catal 221:319
Sherrington DC, Simpson S (1991) J Catal 131:115
Sherrington DC, Simpson S (1993) React Polym 19:13
Miller MM, Sherrington DC (1994) J Chem Soc Perkin Trans 2:2091
Miller MM, Sherrington DC (1995) J Catal 152:368
Ahn JH, Sherrington DC (1996) J Chem Soc Chem Commun p 643
Valente AA, Petrovski Z, Branco LC, Afonso CAM, Pillinger M, Lopez AD, Romão CC, Nunes CD, Gonçalves IS (2004) J Mol Catal A–Chem 218:5
Kühn FE, Zhao J, Abrantes M, Sun W, Afonso CAM, Branco LC, Gonçalves IS, Pillinger M, Romão CC (2005) Tetrahedron Lett 46:47
Kühn FE, Lopes AD, Santos AM, Herdtweck E, Haider JJ, Romão CC, Santos AG (2000) J Mol Catal A–Chem 151:147
Sakthivel A, Zhao J, Kühn FE (2005) Micropor Mesopor Mater 86:341
Abrantes M, Santos AM, Mink J, Kühn FE, Romão CC (2003) Organometallics 22:2112
Gago S, Pillinger M, Valente AA, Santos TM, Rocha J, Gonçalves IS (2004) Inorg Chem 43:5422
Zhao J, Sakthivel A, Santos AM, Kühn FE (2005) Inorg Chim Acta 358:4201
Sakthivel A, Zhao J, Kühn FE (2005) Bull Catal Soc India 4:79
Zhao XS, Lu GQ (1998) J Phys Chem B 102:1556
Tatsumi T, Koyano A, Tanaka Y, Nakata S (1998) Stud Surf Sci Catal 117:143
Miller MM, Sherrington DC (1994) J Chem Soc Chem Commun 55
Miller MM, Sherrington DC (1995) J Catal 152:377
Leinonen S, Sherrington DC, Sneddon A, McLoughlin D, Corker J, Canevali C, Morazzoni F, Reedjik J, Spratt SPD (1999) J Catal 183:251
Song CE, Roh EH (2000) Chem Commun p 837
Li Z, Xia C-G (2003) Tetrahedron Lett 44:2069
Li Z, Xia C-G, Ji M (2003) Appl Cat A–Gen 252:17
Kühn FE, Santos AM, Herrmann WA (2005) Dalton Trans p 2483
Buffon R, Leconte M, Basset J-M, Touroude R, Herrmann WA (1992) J Mol Catal A–Chem 72:139
Buffon R, Choplin A, Leconte M, Basset J-M, Touroude R, Herrmann WA (1992) J Mol Catal A–Chem 72:L7
Buffon R, Auroux A, Lefebvre F, Leconte M, Choplin A, Basset J-M, Herrmann WA (1992) J Mol Catal A–Chem 76:287
Zhu Z, Espenson JH (1997) J Mol Catal A–Chem 121:139
Bouh AO, Espenson JH (2003) J Mol Catal A–Chem 200:43
Li M, Espenson JH (2004) J Mol Catal A–Chem 208:123
Herrmann WA, Kuchler JG, Felixberger JK, Herdtweck E, Wagner W (1988) Anal Chem 27:394
Neumann R, Wang T-J (1997) J Chem Soc Chem Commun p 1915
Dallmann K, Buffon R (2000) Catal Commun 1:9
Nunes CD, Pillinger M, Valente AA, Gonçalves IS, Rocha J, Ferreira P, Kühn FE (2002) Eur J Inorg Chem p 1100
Sakthivel A, Raudaschl-Sieber G, Kühn FE (2006) Dalton Trans p 468
Wang T-J, Li D-C, Bai J-H, Huang M-Y, Jiang Y-Y (1998) J Macromol Sci Pure 35:531
Adam W, Saha-Möller CR, Weichold O (2000) J Org Chem 65:2897
Adam W, Mitchell CM (1996) Angew Chem Int Ed 35:533
Adam W, Mitchell CM, Saha-Möller CR, Weichold O (1999) J Am Chem Soc 121:2097
Saladino R, Carlucci P, Danti MC, Crestini C, Mincione E (2000) Tetrahedron 56:10031
Sica D, Musumeci D, Zollo F, de Marino S (2001) Eur J Org Chem 19:3731
Sica D, Musumeci D, Zollo F, de Marino S (2001) J Chem Soc Perkin Trans 1:1889
Herrmann WA, Wagner W, Flessner UN, Volkhardt U, Komber H (1991) Angew Chem Int Ed 30:1636
Herrmann WA, Fritz-Meyer-Weg DM, Wagner W, Kuchler JG, Weichselbaumer G, Fischer RW (Hoechst AG) (1992) US Patent 155 247
Saladino R, Neri V, Pellicia AR, Caminiti R, Sadun C (2002) J Org Chem 67:1323
Saladino R, Neri V, Pelliccia AR, Mincione E (2003) Tetrahedron 59:7403
Bernini R, Mincione E, Cortese M, Saladino R, Gualandi G, Belfiore MC (2003) Tetrahedron Lett 44:4823
Bianchini G, Crucianelli M, De Angelis F, Neri V, Saladino R (2004) Tetrahedron Lett 45:2351
Bianchini G, Crucianelli M, De Angelis F, Neri V, Saladino R (2005) Tetrahedron Lett 46:2427
Owens GS, Abu-Omar MM (2000) Chem Commun p 1165
Bernini R, Coratti A, Fabrizi G, Goggiamani A (2003) Tetrahedron Lett 44:8991
Rost AMJ, Schneider H, Zoller JP, Herrmann WA, Kühn FE (2005) J Organomet Chem 690:4712
Bein T, Huber C, Moller K, Wu CG, Xu L (1997) Chem Mater 9:2252
Owens GS, Abu-Omar MM (2002) J Mol Catal A–Chem 187:215
Owens GS, Durazo A, Abu-Omar MM (2002) Chem Eur J 8:3053
Acknowledgments
The authors are greatly indebted to the Fonds der Chemischen Industrie and to the Bayerische Forschungsstiftung (postdoctoral grant for C.F.) for financial support. M.A. Fredricks is acknowledged for helping to edit this work.
Author information
Authors and Affiliations
Corresponding author
Editor information
Rights and permissions
Copyright information
© 2006 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Freund, C., Herrmann, W., Kühn, F.E. (2006). Organorhenium and Organomolybdenum Oxides as Heterogenised Catalysts. In: Meyer, F., Limberg, C. (eds) Organometallic Oxidation Catalysis. Topics in Organometallic Chemistry, vol 22. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3418_029
Download citation
DOI: https://doi.org/10.1007/3418_029
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-540-37209-7
Online ISBN: 978-3-540-37210-3
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)