Abstract
When catalytic hydrogenations use parahydrogen instead of normal H2, the NMR signals of reaction products and intermediates can be dramatically enhanced. This phenomenon, called parahydrogen-induced polarization (PHIP), has been used previously to address the mechanisms of H2 activation by transition metal complexes and clusters in solution. At the same time, it is highly desirable to combine this methodology with heterogeneous catalysis. Potential benefits of such combination include the possibility to develop a hypersensitive NMR-based tool for mechanistic studies of heterogeneous catalytic processes as well as to establish an efficient technology for the production of novel contrast agents for in vivo MRI. To achieve this, one needs to combine the ‘homogeneous’ hydrogenation mechanism, which incorporates both H atoms of a H2 molecule into the same product molecule, with the ease of catalyst removal and the possibility to perform the reaction in a continuous mode, the inherent features of heterogeneous catalysis. This field of NMR and MRI research can thus benefit from the current efforts at the interface between homogeneous and heterogeneous catalysis. Here, after a brief introduction of the PHIP phenomenon, the current progress in combining PHIP with heterogeneous hydrogenations is discussed, and future promising directions are outlined.
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Roe DC, Kating PM, Krusic PJ, Smart BE (1998) Top Catal 5:133
Elsevier CJ (1994) J Mol Catal 92:285
Bargon J, Kuhn L (eds) (2007) In situ NMR methods in catalysis. Springer, Heidelberg
Hunger M, Wang W (2006) Adv Catal 50:147
Ivanova II, Kolyagin YG (2010) Chem Soc Rev 39:5018
Blasco T (2010) Chem Soc Rev 39:4685
Belyakov PA, Kadentsev VI, Chizhov AO, Kolotyrkina NG, Shashkov AS, Ananikov VP (2010) Mendeleev Commun 20:125
Lysova AA, Koptyug IV (2010) Chem Soc Rev 39:4585
Koptyug IV (2014) In: Douthwaite R, Duckett S, Yarwood J (eds) Spectroscopic properties of inorganic and organometallic compounds. Royal Society of Chemistry, Cambridge
Gladden LF, Mitchell J (2011) New J Phys 13:035001
Gladden LF (2013) Curr Opinion Chem Eng 2:331
Gladden LF, Mantle MD, Sederman AJ (2006) Adv Catal 50:1
Mantle MD, Sederman AJ (2003) Progr NMR Spectrosc 43:3
Camp JCJ, Mantle MD, York APE, McGregor J (2014) Rev Sci Instr 85:063111
Weckhuysen BM (ed) (2010) Themed issue “In-situ characterization of heterogeneous catalysts”, Chemical Society Reviews, vol 39, issue 12
Sievers C, Bare SR, Stavitski E (eds) (2013) The 4th international congress on operando spectroscopy, Catalysis Today, vol 205
Mansson S, Johansson E, Magnusson P, Chai C-M, Hansson G, Petersson JS, Stahlberg F, Golman K (2006) Eur Radiol 16:57
Kuhn L (ed) (2013) Hyperpolarization methods in NMR spectroscopy. Springer, Berlin, p 138
Kurhanewicz J, Vigneron DB, Brindle K, Chekmenev EY, Comment A, Cunningham CH, DeBerardinis RJ, Green GG, Leach MO, Rajan SS, Rizi RR, Ross BD, Warren WS, Malloy CR (2011) Neoplasia 13:81
Koptyug IV (2013) Mendeleev Commun 23:299
Atsarkin AV, Kockenberger W (eds) (2012) Special issue “the different magnetic resonance communities join forces for progress in DNP”, Applied magnetic resonance, vol 43, Issue 1–2
Coffey AM, Kovtunov KV, Barskiy DA, Koptyug IV, Shchepin RV, Waddell KW, He P, Groome KA, Best QA, Shi F, Goodson BM, Chekmenev EY (2014) Anal Chem 86:9042
Kovtunov KV, Truong ML, Barskiy DA, Koptyug IV, Coffey AM, Waddell KW, Chekmenev EY (2014) Chem Eur J 20:14629
Barskiy DA, Kovtunov KV, Koptyug IV, He P, Groome KA, Best QA, Shi F, Goodson BM, Shchepin RV, Truong ML, Coffey AM, Waddell KW, Chekmenev EY (2014) ChemPhysChem 15:4100
Coffey AM, Truong ML, Chekmenev EY (2013) J Magn Reson 237:169
Hamans BC, Andreychenko A, Heerschap A, Wijmenga SS, Tessari M (2011) J Magn Reson 212:224
Theis T, Ganssle P, Kervern G, Knappe S, Kitching J, Ledbetter MP, Budker D, Pines A (2011) Nat Phys 7:571
Colell J, Turschmann P, Gloggler S, Schleker P, Theis T, Ledbetter M, Budker D, Pines A, Blumich B, Appelt S (2013) Phys Rev Lett 110:137602
Theis T, Ledbetter MP, Kervern G, Blanchard JW, Ganssle PJ, Butler MC, Shin HD, Budker D, Pines A (2012) J Am Chem Soc 134:3987
Blumich B, Casanova F, Dabrowski M, Danieli E, Evertz L, Haber A, Van Landeghem M, Haber-Pohlmeier S, Olaru A, Perlo J, Sucre O (2011) New J Phys 13:015003
Zalesskiy SS, Danieli E, Blumich B, Ananikov VP (2014) Chem Rev 114:5641
Bouchard L-S, Burt SR, Anwar MS, Kovtunov KV, Koptyug IV, Pines A (2008) Science 319:442
Telkki V-V, Zhivonitko VV, Ahola S, Kovtunov KV, Jokisaari J, Koptyug IV (2010) Angew Chem Int Ed 49:8363
Zhivonitko VV, Telkki V-V, Koptyug IV (2012) Angew Chem Int Ed 51:8054
Kobayashi T, Perras FA, Slowing II, Sadow AD, Pruski M (2015) ACS Catal 5:7055
Rossini AJ, Zagdoun A, Lelli M, Lesage A, Coperet C, Emsley L (2013) Acc Chem Res 46:1942
Lesage A, Lelli M, Gajan D, Caporini MA, Mieville P, Alauzun J, Roussey A, Thieuleux C, Mehdi A, Bodenhausen G, Coperet C, Emsley L (2010) J Am Chem Soc 132:15459
Lelli M, Gajan D, Lesage A, Caporini MA, Vitzthum V, Mieville P, Heroguel F, Rascon F, Roussey A, Thieuleux C, Boualleg M, Veyre L, Bodenhausen G, Coperet C, Emsley L (2011) J Am Chem Soc 133:2104
Rossini AJ, Zagdoun A, Lelli M, Canivet J, Aguado S, Ouari O, Tordo P, Rosay M, Maas WE, Coperet C, Farrusseng D, Emsley L, Lesage A (2012) Angew Chem Int Ed 51:123
Johnson RL, Perras FA, Kobayashi T, Schwartz TJ, Dumesic JA, Shanks BH, Pruski M (2016) Chem Commun 52:1859
Gutmann T, Liu J, Rothermel N, Xu Y, Jaumann E, Werner M, Breitzke H, Sigurdsson ST, Buntkowsky G (2015) Chem Eur J 21:3798
Bowers CR, Weitekamp DP (1987) J Am Chem Soc 109:5541
Duckett SB, Wood NJ (2008) Coord Chem Rev 252:2278
Natterer J, Bargon J (1997) Progr NMR Spectrosc 31:293
Canet D, Aroulanda C, Mutzenhardt P, Aime S, Gobetto R, Reineri F (2006) Concepts Magn Reson 28A:321
Kovtunov KV, Zhivonitko VV, Skovpin IV, Barskiy DA, Koptyug IV (2013) Top Curr Chem 338:123
Ananikov VP, Khemchyan LL, Ivanova YuV, Bukhtiyarov VI, Sorokin AM, Prosvirin IP, Vatsadze SZ, Medved’ko AV, Nuriev VN, Dilman AD, Levin VV, Koptyug IV, Kovtunov KV, Zhivonitko VV, Likholobov VA, Romanenko AV, Simonov PA, Nenajdenko VG, Shmatova OI, Muzalevskiy VM, Nechaev MS, Asachenko AF, Morozov OS, Dzhevakov PB, Osipov SN, Vorobyeva DV, Topchiy MA, Zotova MA, Ponomarenko SA, Borshchev OV, Luponosov YN, Rempel AA, Valeeva AA, Stakheev AY, Turova OV, Mashkovsky IS, Sysolyatin SV, Malykhin VV, Bukhtiyarova GA, Terent’ev AO, Krylov IB (2014) Russ Chem Rev 83:885
Golman K, Olsson LE, Axelsson O, Mnsson S, Karlsson M, Petersson JS (2003) Br. J Radiol 76:S118
Terreno E, Castelli DD, Viale A, Aime S (2010) Chem Rev 110:3019
Bhattacharya P, Ross BD, Bunger R (2009) Exp Biol Med 234:1395
Nikolaou P, Goodson BM, Chekmenev EY (2014) Chem Eur J 21:3156
Golman K, Axelsson O, Johannesson H, Mansson S, Olofsson C, Petersson JS (2001) Magn Reson Med 46:1
Johannesson H, Axelsson O, Karlsson M (2004) Comptes Rendus Physique 5:315
Bhattacharya P, Harris K, Lin AP, Mansson M, Norton VA, Perman WH, Weitekamp DP, Ross BD (2005) MAGMA 18:245
Bhattacharya P, Chekmenev EY, Reynolds WF, Wagner S, Zacharias N, Chan HR, Bunger R, Ross BD (2011) NMR Biomed 24:1023
Bhattacharya P, Chekmenev EY, Perman WH, Harris KC, Lin AP, Norton VA, Tan CT, Ross BD, Weitekamp DP (2007) J Magn Reson 186:150
Ross BD, Bhattacharya P, Wagner S, Tran T, Sailasuta N (2010) Am J Neuroradiol 31:24
Zacharias NM, Chan HR, Sailasuta N, Ross BD, Bhattacharya P (2012) J Am Chem Soc 134:934
Kadlecek S, Vahdat V, Nakayama T, Ng D, Emami K, Rizi R (2011) NMR Biomed 24:933
Bowers CR, Weitekamp DP (1986) Phys Rev Lett 57:2645
Pravica MG, Weitekamp DP (1988) Chem Phys Lett 145:255
Green RA, Adams RW, Duckett SB, Mewis RE, Williamson DC, Green GGR (2012) Progr NMR Spectrosc 67:1
Koch A, Bargon J (2001) Inorg Chem 40:533
Duckett SB, Sleigh CJ (1999) Progr NMR Spectrosc 34:71
Zhivonitko VV, Telkki V-V, Chernichenko K, Repo TJ, Leskela M, Sumerin V, Koptyug IV (2014) J Am Chem Soc 136:598
Longobardi LE, Russell CA, Green M, Townsend NS, Wang K, Holmes AJ, Duckett SB, McGrady JE, Stephan DW (2014) J Am Chem Soc 136:13453
Nelson SJ, Kurhanewicz J, Vigneron DB, Larson PEZ, Harzstark AL, Ferrone M, van Criekinge M, Chang JW, Bok R, Park I, Reed G, Carvajal L, Small EJ, Munster P, Weinberg VK, Ardenkjaer-Larsen JH, Chen AP, Hurd RE, Odegardstuen L-I, Robb FJ, Tropp J, Murray JA (2013) Sci Transl Med 5:198ra108
Corma A (2004) Catal Rev 46:369
Kirschning A (ed) (2004) Immobilized catalysts: solid phases, immobilization and applications. Springer, Heidelberg
Li C, Liu Y (eds) (2014) Bridging heterogeneous and homogeneous catalysis. Concepts, strategies, and applications. Wiley, New Jersey
Kovtunov KV, Koptyug IV (2008) In: Codd S, Seymour JD (eds) Magnetic Resonance Microscopy: Spatially Resolved NMR Techniques and Applications. Wiley, New Jersey
Zhivonitko VV, Kovtunov KV, Skovpin IV, Barskiy DA, Salnikov OG, Koptyug IV (2014) In: Ananikov VP (ed) Understanding organometallic reaction mechanisms and catalysis. Wiley, New Jersey
Barbaro P, Bianchini C (2002) Top Catal 19:17
Cole-Hamilton DJ, Tooze RP (eds) (2006) Catalysis by metal complexes, vol. 30, catalyst separation, recovery and recycling: chemistry and process design. Springer, Dordrecht
End N, Schoning K-U (2004) Top Curr Chem 242:241
Merckle C, Blumel J (2005) Top Catal 34:5
Wegener SL, Marks TJ, Stair PC (2012) Acc Chem Res 45:206
Koptyug IV, Kovtunov KV, Burt SR, Anwar MS, Hilty C, Han S, Pines A, Sagdeev RZ (2007) J Am Chem Soc 129:5580
Jones C (2010) Top Catal 53:942
Gutmann T, Ratajczyk T, Xu Y, Breitzke H, Grunberg A, Dillenberger S, Bommerich U, Trantzschel T, Bernarding J, Buntkowsky G (2010) Solid State NMR 38:90
Abdulhussain S, Breitzke H, Ratajczyk T, Grunberg A, Srour M, Arnaut D, Weidler H, Kunz U, Kleebe HJ, Bommerich U, Bernarding J, Gutmann T, Buntkowsky G (2014) Chem Eur J 20:1159
Skovpin IV, Zhivonitko VV, Koptyug IV (2011) Appl Magn Reson 41:393
Skovpin IV, Zhivonitko VV, Kaptein R, Koptyug IV (2013) Appl Magn Reson 44:289
Adams RW, Aguilar JA, Atkinson KD, Cowley MJ, Elliott PIP, Duckett SB, Green GGR, Khazal IG, Lopez-Serrano J, Williamson DC (2009) Science 323:1708
Fekete M, Bayfield OW, Duckett SB, Hart S, Mewis RE, Pridmore N, Rayner PJ, Whitwood A (2013) Inorg Chem 52:13453
Shi F, Coffey AM, Waddell KW, Chekmenev EY, Goodson BM (2015) J Phys Chem C 119:7525
Kovtunov KV, Zhivonitko VV, Corma A, Koptyug IV (2010) J Phys Chem Lett 1:1705
Zhang X, Llabres i Xamena FX, Corma A (2009) J Catal 265:155
Gutmann T, Sellin M, Breitzke H, Stark A, Buntkowsky G (2009) Phys Chem Chem Phys 11:9170
Mehnert CP, Mozeleski EJ, Cook RA (2002) Chem Commun 24:3010
Virtanen P, Salmi T, Mikkola J-P (2009) Ind Eng Chem Res 48:10335
Gong Q, Klankermayer J, Blumich B (2011) Chem Eur J 17:13795
Horiuti I, Polanyi M (1934) Trans Faraday Soc 30:1164
Cremer PS, Su X, Shen YR, Somorjai GA (1996) J Phys Chem 100:16302
Eichhorn A, Koch A, Bargon J (2001) J Mol Catal A 174:293
Kovtunov KV, Beck IE, Bukhtiyarov VI, Koptyug IV (2008) Angew Chem Int Ed 47:1492
Salnikov OG, Kovtunov KV, Barskiy DA, Bukhtiyarov VI, Kaptein R, Koptyug IV (2013) Appl Magn Reson 44:279
Zhou R, Zhao EW, Cheng W, Neal LM, Zheng H, Quinones RE, Hagelin-Weaver HE, Bowers CR (2015) J Am Chem Soc 137:1938
Kovtunov KV, Truong ML, Barskiy DA, Salnikov OG, Bukhtiyarov VI, Coffey AM, Waddell KW, Koptyug IV, Chekmenev EY (2014) J Phys Chem C 118:28234
Zhou R, Cheng W, Neal LM, Zhao EW, Ludden K, Hagelin-Weaver HE, Bowers CR (2015) Phys Chem Chem Phys 17:26121
Kovtunov KV, Beck IE, Zhivonitko VV, Barskiy DA, Bukhtiyarov VI, Koptyug IV (2012) Phys Chem Chem Phys 14:11008
Dupont J, Fonseca GS, Umpierre AP, Fichtner PFP, Teixeira SR (2002) J Am Chem Soc 124:4228
Ruta M, Laurenczy G, Dyson PJ, Kiwi-Minsker L (2008) J Phys Chem C 112:17814
Kovtunov KV, Zhivonitko VV, Kiwi-Minsker L, Koptyug IV (2010) Chem Commun 46:5764
Barskiy DA, Kovtunov KV, Primo A, Corma A, Kaptein R, Koptyug IV (2012) ChemCatChem 4:2031
Salnikov OG, Barskiy DA, Burueva DB, Gulyaeva YK, Balzhinimaev BS, Kovtunov KV, Koptyug IV (2014) Appl Magn Reson 45:1051
Koptyug IV, Zhivonitko VV, Kovtunov KV (2010) ChemPhysChem 11:3086
Balu AM, Duckett SB, Luque R (2009) Dalton Trans 26:5074
Zhivonitko VV, Kovtunov KV, Beck IE, Ayupov AB, Bukhtiyarov VI, Koptyug IV (2011) J Phys Chem C 115:13386
Barskiy DA, Salnikov OG, Kovtunov KV, Koptyug IV (2015) J Phys Chem A 119:996
Kovtunov KV, Barskiy DA, Salnikov OG, Burueva DB, Khudorozhkov AK, Bukhtiyarov AV, Prosvirin IP, Gerasimov EY, Bukhtiyarov VI, Koptyug IV (2015) ChemCatChem 7:2581
Zhao EW, Zheng H, Ludden K, Xin Y, Hagelin-Weaver HE, Bowers CR (2016) ACS Catal 6:974
Teschner D, Vass E, Havecker M, Zafeiratos S, Schnorch P, Sauer H, Knop-Gericke A, Schlogl R, Chamam M, Wootsch A, Canning AS, Gamman JJ, Jackson SD, McGregor J, Gladden LF (2006) J Catal 242:26
Somorjai GA, Zaera F (1982) J Phys Chem 86:3070
Bond GC (1997) Appl Catal A 149:3
Wasylenko W, Frei H (2005) J Phys Chem B 109:16873
Cremer PS, Su X, Shen YR, Somorjai GA (1996) J Am Chem Soc 118:2942
Sharma R, Bouchard LS (2012) Sci. Rep. 2:277
Gloggler S, Grunfeld AM, Ertas YN, McCormick J, Wagner S, Schleker PPM, Bouchard L-S (2015) Angew Chem Int Ed 54:2452
Irfan M, Eshuis N, Spannring P, Tessari M, Feiters MC, Rutjes FPJT (2014) J Phys Chem C 118:13313
Vile G, Baudouin D, Remediakis IN, Coperet C, Lopez N, Perez-Ramirez J (2013) ChemCatChem 5:3750
Twigg GH (1950) Discuss Faraday Soc 8:152
Twigg GH, Rideal EK (1939) Proc R. Soc London 171:55
Harrison DL, Nicholls D, Steiner H (1967) J Catal 7:359
Conner WC, Kokes RJ (1969) J Phys Chem 73:2436
Tanaka Y, Hattori H, Tanabe K (1976) Chem Lett 5:37
Kovtunov KV, Barskiy DA, Salnikov OG, Khudorozhkov AK, Bukhtiyarov VI, Prosvirin IP, Koptyug IV (2014) Chem Commun 50:875
Salnikov OG, Kovtunov KV, Barskiy DA, Khudorozhkov AK, Inozemtseva EA, Prosvirin IP, Bukhtiyarov VI, Koptyug IV (2014) ACS Catal 4:2022
Shapira Y, Becerra CC (1976) Phys Lett A 59:75
Vile G, Bridier B, Wichert J, Perez-Ramirez J (2012) Angew Chem Int Ed 51:8620
Garcia-Melchor M, Bellarosa L, Lopez N (2014) ACS Catal. 4:4015
Zhao EW, Zheng H, Zhou R, Hagelin-Weaver HE, Bowers CR (2015) Angew Chem Int Ed 54:14270
Liang S, Hao C, Shi Y (2015) ChemCatChem 7:2559
Corma A, Salnikov OG, Barskiy DA, Kovtunov KV, Koptyug IV (2015) Chem Eur J 21:7012
Henning H, Dyballa M, Scheibe M, Klemm E, Hunger M (2013) Chem Phys Lett 555:258
Arzumanov SS, Stepanov AG (2013) J Phys Chem C 117:2888
Carson PJ, Bowers CR, Weitekamp DP (2001) J Am Chem Soc 123:11821
Buntkowsky G, Gutmann T, Petrova MV, Ivanov KL, Bommerich U, Plaumann M, Bernarding J (2014) Solid State NMR 63:20
Salnikov OG, Burueva DB, Barskiy DA, Bukhtiyarova GA, Kovtunov KV, Koptyug IV (2015) ChemCatChem 7:3508
Zhivonitko VV, Kovtunov KV, Chapovsky PL, Koptyug IV (2013) Angew Chem Int Ed 52:13251
Levitt MH (2012) Annu Rev Phys Chem 63:89
Stevanato G, Hill-Cousins JT, Hakansson P, Roy SS, Brown LJ, Brown RCD, Pileio G, Levitt MH (2015) Angew Chem Int Ed 54:3740
Pileio G, Bowen S, Laustsen C, Tayler MCD, Hill-Cousins JT, Brown LJ, Brown RCD, Ardenkjaer-Larsen JH, Levitt MH (2013) J Am Chem Soc 135:5084
Warren WS, Jenista E, Branca RT, Chen X (2009) Science 323:1711
Vasos PR, Comment A, Sarkar R, Ahuja P, Jannin S, Ansermet J-P, Konter JA, Hautle P, Van Den Brandt B, Bodenhausen G (2009) Proc Natl Acad Sci USA 106:18469
Franzoni MB, Buljubasich L, Spiess HW, Munnemann K (2012) J Am Chem Soc 134:10393
Vinogradov E, Grant AK (2008) J Magn Reson 194:46
Salnikov OG, Kovtunov KV, Koptyug IV (2015) Sci Rep 5:13930
Acknowledgments
The authors from ITC thank Russian Science Foundation (RSF; Grant 14-13-00445) for financial support of the studies of catalytic hydrogenation with parahydrogen and of the NMR experiments. VIB thanks RSF (Grant #14-23-00146) for supporting the preparation and characterization of heterogeneous catalysts. The basic funding was provided by FASO (project # 0333-2014-0001).
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Kovtunov, K.V., Salnikov, O.G., Zhivonitko, V.V. et al. Catalysis and Nuclear Magnetic Resonance Signal Enhancement with Parahydrogen. Top Catal 59, 1686–1699 (2016). https://doi.org/10.1007/s11244-016-0688-6
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DOI: https://doi.org/10.1007/s11244-016-0688-6