Georgiy B. Shul'pin

Georgiy Borisovich Shul’pin (Russian: Георгий Борисович Шульпи́н, also Shulpin) was born in 1946 in Moscow, Russia. He graduated with a M.S. degree in chemistry from the Chemistry Department of Moscow State University in 1969. Between 1969 and 1972, he was a postgraduate student at the Nesmeyanov Institute of Organoelement Compounds (Academy of Sciences of the USSR, Moscow) under the direction of Prof. A. N. Nesmeyanov and received his Ph.D. in organometallic chemistry in 1975.[1] He received his Dr. of Sciences degree in 2013.

Career

Since 1978, Shul’pin has been working at the N. N. Semenov Institute of Chemical Physics at the Russian Academy of Sciences in Moscow. He is currently a senior scientific researcher. His research activities concern metal complex catalysis,[2] oxidation of hydrocarbons,[3][4] particularly using “green oxidants” H2O2[5] and O2,[6] activation[7] and functionalization[8][9][10][11] of C–H bonds in saturated and aromatic hydrocarbons, organometallic chemistry. Other interests include photocatalysis,[12] biomimetic oxidations[13] and ecological chemistry.

In eighties Shul’pin together with A.E. Shilov discovered the metalation reaction of arenes by hexachloroplatinate which is stimulated by heating, light or gamma-irradiation[14][15][16][17][18][19][20] and affords stable sigma-aryl Pt(IV) complexes (“Shul’pin’s reaction”).[21]

He developed aerobic oxygenation of saturated hydrocarbons under visible light irradiation catalyzed by oxo and chloride complexes of transition metals[22] and discovered three efficient systems for the catalytic oxidations with hydrogen peroxide. Catalytic combinations: i) “vanadium derivative plus pyrazine-2-carboxylic acid (PCA)”;[23][24][25][26][27][28] ii) “a dinuclear manganese(IV) complex plus carboxylic acid”;[29][30] iii) “an osmium complex plus amine”.[31]

G. B. Shul’pin proposed a simple and convenient method for the estimation of concentration of alkyl hydroperoxides formed in alkane oxidations by molecular oxygen or peroxides. This method (gas-chromatographic analysis of the samples before and after their reduction by triphenylphosphine, “Shul’pin’s method”) is widely used in chemical practice.[32][33][34][35][36][37]

G. B. Shul’pin has published about 250 papers in chemical journals. He is the author (coauthor) of monographs[38][39][40][41] and reviews.[42][43][44][45][46] He has also written numerous books on popular science (for example,[47][48][49][50]) and articles in popular scientific journals.

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References
  1. Smith, M.B.; March, J. (2007). March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure. New Jersey: J. Wiley & Sons, Inc. p. 66. ISBN 978-0-471-72091-1. Retrieved 2010-11-30.
  2. B. Plietker (Ed.), “Iron Catalysis in Organic Chemistry: Reactions and Applications”, WILEY-VCH, Weinheim, 2008, pp. 77, 80. ISBN 978-3-527-31927-5
  3. W. Carruthers, I. Coldham, “Modern methods of organic synthesis”, Fourth edition, Cambridge University Press, 2004, p. 371. ISBN 0-521-77097-1 https://books.google.com/books?id=7gPnWf4UDLsC&printsec=frontcover&dq=W.+Carruthers,+I.+Coldham,+%E2%80%9CModern+methods+of+organic+synthesis%E2%80%9D,&source=bl&ots=tz9VK72O1x&sig=zZiihLSWEboZeiyALlziAqkfwDI&hl=ru&ei=jVoYTZufMISSOpbEsIIJ&sa=X&oi=book_result&ct=result&resnum=1&sqi=2&ved=0CBcQ6AEwAA#v=onepage&q&f=false
  4. R. H. Crabtree (Ed.), “Energy Production and Storage: Inorganic Chemical Strategies for a Warming World”, J. Wiley & Sons, Inc., Chichester, West Sussex, 2010. Chapter (pp. 101-142): B. G. Hashiguchi, C. H. Hövelmann, S. M. Bischof, K. S. Lokare, C. H. Leung, R. A. Periana, “Methane-to-Methanol Conversion”, pp. 11-113, 131, 134, 137. ISBN 978-0-470-74986-9
  5. W. R. Sanderson, “Hydrogen Peroxide in Waste Minimisation – Current and Potential Contributions”, in: J. H. Clark, D. J. Macquarrie (Eds.), “Handbook of Green Chemistry and Technology”, Blackwell, Oxford, 2002, Chapter11, pp. 258-305. ISBN 0-632-05715-7
  6. F. Cavani, S. Alini, “Synthesis of Adipic Acid: On the Way to More Sustainable Production”, Chapter 7 in: F. Cavani, G. Centi, S. Perathoner, F. Trifiró (Eds.), “Sustainable Industrial Chemistry”, WILEY-VCH, Weinheim, 2009. ISBN 978-3-527-31552-9
  7. T. B. Gunnoe, “Metal-Mediated Carbon-Hydrogen Bond Activation”, Chapter 11 in: A. Bacac (Ed.), “Physical Inorganic chemistry: Reactions, Processes, and Applications”, J. Wiley & Sons, Inc., New Jersey, 2010, pp. 495-550. ISBN 978-0-470-22420-5
  8. P. W. N. M. van Leeuwen, “Homogeneous Catalysis: Understanding the Art”, Kluwer, Dordrecht, 2004, Chapter 19 (“C-H Functionalization”). ISBN 1-4020-1999-8
  9. R. B. King, “Encyclopedia of Inorganic Chemistry: S”, Second Edition, J. Wiley & Sons, Inc., 2005, p. 4381. ISBN 978-0-470-86078-6
  10. C.-J. Li, T.-H. Chan, “Comprehensive Organic Reactions in Aqueous Media”, J. Wiley & Sons, Inc., New Jersey, 2007, ISBN 978-0-471-76129-7
  11. J.-Q. Yu, Z. Shi (Eds.), “C-H Activation”, Springer, Heidelberg, 2010. doi:10.1007/978-3-642-12356-6
  12. T. Bitterwolf, “Photochemistry of Transition Metal Complexes”, in: “Encyclopedia of Inorganic Chemistry”, Wiley Online Library, 2006, Online ISBN 978-0-470-86210-0 doi:10.1002/0470862106.ia189
  13. S. Tanase, E. Boluwman, “Selective Conversion of Hydrocarbons with H2O2 Using Biomimetic Non-heme Iron and Manganese Oxidation Catalysts”, in: R. Van Eldik, J. Reedijk (Eds.), “Adv. Inorg. Chem.: Homogeneous Biomimetic Oxidation Catalysis”, vol. 58, Academic Press, London, 2006, pp. 55, 63, 70. ISBN 978-0-12-023658-9
  14. R. H. Crabtree, “The organometallic chemistry of alkanes”, Chem. Rev. 1985, 85, 245-269. doi:10.1021/cr00068a002
  15. V. K. Jain, G. S. Rao, L. Jain, “The Organic Chemistry of Platinum(IV)”, in: “Advances in Organometallic Chemistry”, vol. 27, Academic Press, Inc., 1987, p. 116. ISBN 0-12-031127-5
  16. G. K. Anderson, “Platinum-Carbon sigma-Bonded Complexes”, in: R. J. Puddephatt (Ed.), “Comprehensive Organometallic Chemistry II”, Elsevier, 1995, p. 518. ISBN 0-08-042316-7
  17. L. Johansson, O. B. Ryan, C. Rømming, M. Tilset, “Unexpected Selectivities in C-H Activations of Toluene and p-Xylene at Cationic Platinum(II) Diimine Complexes.”, J. Am. Chem. Soc. 2001, 123, 6579-6590. doi:10.1021/ja010277e
  18. J. Mamtora, S. H. Crosby, C. P. Newman, G. J. Clarkson, J. P. Rourke, “Platinum(IV) Complexes: C-H Activation at Low Temperatures”, Organometallics 2008, 27, 5559–5565. doi:10.1021/om800583c
  19. A. M. Voutchkova, R. H. Crabtree, J. Mol. Catal., A: Chem. 2009, 312, 1-6. doi:10.1016/j.molcata.2009.07.019
  20. P. Sehnal, R. J. K. Taylor, I. J. S. Fairlamb, “Emergence of Palladium(IV) Chemistry in Synthesis and Catalysis”, Chem. Rev. 2010, 110, 824–889. doi:10.1021/cr9003242
  21. M. Ochiai, K. Fukui, S. Iwatsuki, K. Ishihara, K. Matsumoto, “Synthesis of aryl-platinum dinuclear complexes via ortho C-H bond activation of phenol and transmetalation of arylboronic acid”, Organometallics, 2005, 24, 5528-5536. doi:10.1021/om050316l
  22. J.-E. Bäckvall (Ed.), “Modern Oxidation Methods”, WILEY-VCH Verlag, Weinheim, 2004, p. 121. ISBN 3-527-30642-0 http://www.wiley-vch.de/publish/en/books/bySubjectCH00/ISBN3-527-30642-0/?sID=8245b6d09961810d71a72151875fb5a1
  23. P. P. Knops-Gerrits, C. A. Trujillo, B. Z. Zhan, X. Y. Li, P. Rouxhet, P. A. Jacobs, “Oxidation catalysis with well-characterised vanadyl bis-bipyridine complexes encapsulated in NaY zeolite”, Topics in Catalysis, 1996, 437-449. doi:10.1007/BF02113866
  24. W. A. Herrmann (Ed.), “Synthetic Methods of Organometallic and Inorganic Chemistry: Catalysis (Herrmann/Brauer, vol. 10: Catalysis)”, Georg Thieme Verlag, Stuttgart, 2002, Chapter 10, pp. 117-121. ISBN 3-13-115161-7
  25. G. A. Olah, A. Molnár, “Hydrocarbon Chemistry”, Second edition, J. Wiley & Sons, Inc., New Jersey, 2003, pp. 520 and 565. ISBN 0-471-41782-3 doi:10.1002/0471433489 http://www.wiley-vch.de/publish/en/books/bySubjectCH00/ISBN0-471-41782-3/?sID=8245b6d09961810d71a72151875fb5a1
  26. J.-E. Bäckvall (Ed.), “Modern Oxidation Methods”, WILEY-VCH Verlag, Weinheim, 2004, p. 121. ISBN 3-527-30642-0
  27. R. Z. Khaliullin, A. T. Bell, M. Head-Gordon, “A Density Functional Theory Study of the Mechanism of Free Radical Generation in the System Vanadate/PCA/H2O2”, J. Phys. Chem. B 2005, 109, 17984-17992. doi:10.1021/jp058162a
  28. Z. Rappoport (Ed.), “The Chemistry of Peroxides”, J. Wiley & Sons, Inc., 2006, p. 1116. ISBN 978-0-470-86274-2
  29. K. F. Sibbons, K. Shastri, M. Watkinson, “The application of manganese complexes of ligands derived from 1,4,7-triazacyclononane in oxidative catalysis (a review)”, Dalton Trans. 2006, 645-661. doi:10.1039/b511331h
  30. “Alkanes: Webster’s Facts and Phrases”, ICON, San Diego, 2008, p. 41. ISBN 0-546-67675-8
  31. G. A. Olah, A. Molnár, “Hydrocarbon Chemistry”, Second edition, J. Wiley & Sons, Inc., New Jersey, 2003, pp. 521 and 566. ISBN 0-471-41782-3. doi:10.1002/0471433489 http://www.wiley-vch.de/publish/en/books/bySubjectCH00/ISBN0-471-41782-3/?sID=8245b6d09961810d71a72151875fb5a1
  32. Q. Yuan, W. Deng, Q. Zhang, Y. Wang, “Osmium-catalyzed selective oxidations of methane and ethane with hydrogen peroxide in aqueous medium”, Adv. Synth. Catal. 2007, 349, 1199–1209. doi:10.1002/adsc.200600438
  33. L. Zhou, Y. Chen, X. Yang, Y. Su, W. Zhang, J. Xu, “Electronic effect of substituent of quinones on their catalytic performance in hydrocarbons oxidation”, Catal. Let. 2008, 125, 154-159. doi:10.1007/s10562-008-9537-y
  34. G. S. Mishra, T. F. S. Silva, L. M. D. R. S. Martins, A. J. L. Pombeiro,”Scorpionate complexes of vanadium(III or IV) as catalyst precursors for solvent-free cyclohexane oxidation with dioxygen”, Pure Appl. Chem., 2009, 81, 1217–1227. doi:10.1351/PAC-CON-08-10-08
  35. K. T. Mahmudov, M. N. Kopylovich, M. F. C. G. da Silva, P. J. Figiel, Y. Y. Karabach, A. J. L. Pombeiro, “New copper(II) dimer and its catalytic activity in cyclohexane and benzyl alcohol oxidations”, J. Mol. Catal., A: Chem. 2010, 318, 44-50. doi:10.1016/j.molcata.2009.11.006
  36. P. Roy, M. Manassero, “Tetranuclear copper(II)–Schiff-base complexes as active catalysts for oxidation of cyclohexane and toluene”, Dalton Trans. 2010, 1539-1545. doi:10.1039/b914017d
  37. S. Bose, A. Pariyar, A. N. Biswas, P. Das, P. Bandyopadhyay, “Mild oxidation of hydrocarbons by tert-butyl hydroperoxide catalyzed by electron deficient manganese(III) corroles”, J. Mol. Catal., A: Chem. 2010, 332, 1-6 doi:10.1016/j.molcata.2010.09.001.
  38. S. P. Gubin, G. B. Shul’pin, “The Chemistry of Complexes with Metal-Carbon Bonds”, Novosibirsk, Nauka, 1984, 280 pp. (in Russian).
  39. G. B. Shul’pin, “Organic Reactions Catalyzed by Metal Complexes”, Nauka, Moscow, 1988 (285 pp., in Russian). ISBN 5-02-001351-X
  40. A. E. Shilov, G. B. Shul’pin, “Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes”, Kluwer Academic Publishers, Dordrecht/Boston/London, 2000, (548 pp.) (Springer, ISBN 978-0-7923-6101-5) https://www.springer.com/chemistry/physical+chemistry/book/978-0-7923-6101-5
  41. G. B. Shul’pin, “Oxidations of C–H Compounds Catalyzed by Metal Complexes”, in: "Transition Metals for Organic Synthesis", Eds. M. Beller, C. Bolm, Second Edition, WILEY-VCH Verlag, Weinheim, 2004, Vol. 2, Chapter 2.2, pp. 215–241. ISBN 3-527-30613-7, ISBN 978-3-527-30613-8
  42. A. E. Shilov, G. B. Shul’pin, “Activation of C–H Bonds by Metal Complexes”, Chem. Rev. 1997, 97(8), 2879–2932. doi:10.1021/cr9411886
  43. G. B. Shul’pin, "Metal-catalysed hydrocarbon oxygenations in solutions: the dramatic role of additives: a review", J. Mol. Catal. A: Chem. 2002, 189, 39–66. doi:10.1016/S1381-1169(02)00196-6
  44. G. B. Shul’pin, "Metal-catalysed hydrocarbon oxidations", Comptes Rendus, Chimie 2003, 6, 163–178. doi:10.1016/S1631-0748(03)00021-3
  45. G. B. Shul’pin, “Hydrocarbon Oxygenations with Peroxides Catalyzed by Metal Compounds”, Mini-Rev. Org. Chem. 2009, 6, 95–104.
  46. G. B. Shul’pin, “Selectivity enhancement in functionalization of C–H bonds: A review”, Org. Biomol. Chem. 2010, 8, 4217–4228. doi:10.1039/c004223d
  47. G. B. Shul'pin, The World of Unusual Molecules: Organometallic Complexes, Moscow, Nauka, 1986, 176 pp. (in Russian).
  48. G. B. Shul'pin, Learning About Chemistry, Moscow, Mir Publishers, 1989, 232 pp. (in English). ISBN 5-03-000542-0
  49. C. Shulpin, Que es la quimica organica, Ediciones Quinto Sol, Mexico, 1988, 272 pp. (in Spanish). ISBN 968-6136-46-0
  50. G. B. Shulpin, Quimica para todos, Moscu, Editorial Mir, 1990, 264 pp. (in Spanish). ISBN 5-03-001313-X
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