Georgiy B. Shul'pin Explained

Georgiy Borisovich Shul’pin (Russian: Георгий Борисович Шульпи́н, also Shulpin, 22 July 1946 – 3 March 2023) was born 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.

Notes and References

  1. Book: Smith . M.B. . March . J. . March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure . J. Wiley & Sons, Inc. . 2007 . New Jersey . 66 . 2010-11-30 . 978-0-471-72091-1.
  2. B. Plietker (Ed.), “Iron Catalysis in Organic Chemistry: Reactions and Applications”, WILEY-VCH, Weinheim, 2008, pp. 77, 80.
  3. Book: Carruthers . J.E. . Carruthers . W. . Coldham . I. . Modern Methods of Organic Synthesis . Cambridge University Press . Cambridge texts in chemistry and biochemistry . 2004 . 978-0-521-77830-5 . 26 August 2022 .
  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.
  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.
  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.
  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.
  8. P. W. N. M. van Leeuwen, “Homogeneous Catalysis: Understanding the Art”, Kluwer, Dordrecht, 2004, Chapter 19 (“C-H Functionalization”).
  9. R. B. King, “Encyclopedia of Inorganic Chemistry: S”, Second Edition, J. Wiley & Sons, Inc., 2005, p. 4381.
  10. C.-J. Li, T.-H. Chan, “Comprehensive Organic Reactions in Aqueous Media”, J. Wiley & Sons, Inc., New Jersey, 2007,
  11. J.-Q. Yu, Z. Shi (Eds.), “C-H Activation”, Springer, Heidelberg, 2010.
  12. T. Bitterwolf, “Photochemistry of Transition Metal Complexes”, in: “Encyclopedia of Inorganic Chemistry”, Wiley Online Library, 2006, Online
  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.
  14. R. H. Crabtree, “The organometallic chemistry of alkanes”, Chem. Rev. 1985, 85, 245-269.
  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.
  16. G. K. Anderson, “Platinum-Carbon sigma-Bonded Complexes”, in: R. J. Puddephatt (Ed.), “Comprehensive Organometallic Chemistry II”, Elsevier, 1995, p. 518.
  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.
  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.
  19. A. M. Voutchkova, R. H. Crabtree, J. Mol. Catal., A: Chem. 2009, 312, 1-6.
  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.
  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.
  22. J.-E. Bäckvall (Ed.), “Modern Oxidation Methods”, WILEY-VCH Verlag, Weinheim, 2004, p. 121. 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.
  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.
  25. G. A. Olah, A. Molnár, “Hydrocarbon Chemistry”, Second edition, J. Wiley & Sons, Inc., New Jersey, 2003, pp. 520 and 565. 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.
  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.
  28. Z. Rappoport (Ed.), “The Chemistry of Peroxides”, J. Wiley & Sons, Inc., 2006, p. 1116.
  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.
  30. “Alkanes: Webster’s Facts and Phrases”, ICON, San Diego, 2008, p. 41.
  31. G. A. Olah, A. Molnár, “Hydrocarbon Chemistry”, Second edition, J. Wiley & Sons, Inc., New Jersey, 2003, pp. 521 and 566. . 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.
  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.
  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.
  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.
  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.
  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 .
  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).
  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,) 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.,
  42. A. E. Shilov, G. B. Shul’pin, “Activation of C–H Bonds by Metal Complexes”, Chem. Rev. 1997, 97(8), 2879–2932.
  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.
  44. G. B. Shul’pin, "Metal-catalysed hydrocarbon oxidations", Comptes Rendus, Chimie 2003, 6, 163–178.
  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.
  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).
  49. C. Shulpin, Que es la quimica organica, Ediciones Quinto Sol, Mexico, 1988, 272 pp. (in Spanish).
  50. G. B. Shulpin, Quimica para todos, Moscu, Editorial Mir, 1990, 264 pp. (in Spanish).

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