Nesmejanov, Aleksandr Nikolaevich
NESMEJANOV, ALEKSANDR NIKOLAEVICH
(b. Moscow, Russia, 9 September (28 August old Russian style) 1899; d. Moscow, U.S.S.R., 17 January 1980)
chemistry, organometallic chemistry.
Nesmejanov specialized in developing methods of synthesis and studying properties of organometallic compounds; developing new organic syntheses based on reactions of β-chlorvinylketones and polyhalogenated aliphatic compounds; understanding the dual reactivity and stereochemistry of electrophilic substitution; and developing methods to create artificial foods.
Early Research His father, Nikolai Vasilyevich Nesmejanov, a graduate of the law faculty of Moscow University, was a principal at an orphanage. His mother, Luidmila Danilovna Nesmejanova , who was also involved in teaching, had a talent for painting and decorative arts. Under his mother’s influence Nesmejanov was attracted to botany and natural sciences in general since childhood. In 1908, he entered a private gymnasium (secondary school), while studying Latin and Greek with his father in the evenings. In 1917, he started his university studies in the Physics and Mathematics Faculty of Moscow University. He worked all through his university years: as a night guard in the Chemistry Faculty and as a laboratory assistant in the Military Pedagogical Academy. In 1922, Nesmejanov graduated with a degree in physical chemistry, and accepted Nikolay D. Zelinsky’s offer of a position in the Department of Organic Chemistry to prepare for a doctoral degree.
Zelinsky gave his protégé a topic for his first scientific research, a study of the derivatives of cyclopropane. After a few years of investigation, Nesmejanov created his own task: to find esters of complex acids of type HHgII I3 and HPbII I2.
Nesmejanov’s interest in mercury compounds was connected to his experience in a chemical pesticide laboratory where he served as a technician in the late 1920s. As is well known, many mercury compounds were used to protect seeds from pests. Nesmejanov was forced to work in appalling conditions—there was one desk and a single fume hood for the entire laboratory. Evenings he spent fighting rats. According to his assistant, Nesmejanov worked in the lab “very bravely: for example, he heated a bulb of organic material over an open flame, … however if solvent vapors caught fire he always managed to extinguish it, by blowing on it” (Makarova, 1988, p. 192).
It was known that attempts to combine, for example, CH3 I and HgI2 directly came to nothing. The young scientist then decided to decompose phenyldiazonium salts of the abovementioned complex acids. Successful decomposition of [C6 H5 N2]HgI3 in 1929 led to development of a new general synthetic approach in organic chemistry: obtaining organometallic compounds by decomposing double diazonium salts with metal halides (“Nesmejanov’s diazomethod”). This method allowed for introduction of a metal atom into a predetermined position in an organic molecule. With aid of this technique scientists were able to synthesize many organometallic compounds, which in turn served as parent substances for preparing various classes of hetero-organic compounds (i.e., compounds with metal-carbon bonds).
During the 1935–1948 period, Nesmejanov and his students investigated many ways of interconverting various organometallic compounds, particularly mutual transitions between organomercurials and organic compounds of main group metals such as magnesium, zinc, cadmium, aluminum, thallium, and tin. The wide array of experimental data that was assembled during the course of these investigations led to a relationship between the position of an element in the periodic table and its ability to form organic derivatives.
Nesmejanov also studied geometrical isomerism in organometallic derivatives of ethylene. He was able to produce β-chlorvinyl derivatives of elements such as mercury, antimony, tin, and tantalum in a pure state. This work led to one of the most important rules of stereo-chemistry, that of retention of stereochemical configuration in processes of electrophilic and radical substitution at the carbon atom of the carbon–carbon double bond.
Nesmejanov also paid particular attention to the properties and structures of addition products of transition metal salts and nonmetal halogenides to unsaturated organic compounds. He proved that such products are true hetero-organic compounds (i.e., they have metal–carbon bonds).
From 1950 to 1959, Nesmejanov conducted a series of field studies of βchlorvinylketones chemistry (together with Nikolai K. Kochetkov and Margarita I. Rubinskaya), and of organophosphorus, organofluorine and organo-magnesium compounds. In 1960, he discovered the phenomenon of metallotropy: the reversible transfer of an organomercury unit between hydroxy and nitroso groups in paranitrosophenol.
In addition to issues concerning organic synthesis, Nesmejanov spent a lot of time on the theory of organic chemistry. For example, it was known that metals and their salts could add to multiple carbon-carbon bond, for example
HC≡CH + HgCl2→ ClCH=CHHgCl.
Nesmejanov called the resulting compounds quasi-complex compounds. A key characteristic of such compounds was their dual reactivity, i.e. their ability, when bound with different, and sometimes even with the same reagents, to produce products of different structural types. For example:
ClCH=CHHgCl + HBr → ClCH=CH 2+ HgClBr, ClCH=CHHgCl + 3KJ →
C2 H2 + KHgl3 + 2KCl.
Theoretically, one of the reasons for such behavior of the quasi-complex compounds could be the existence of an equilibrium between organometallic and additive compounds of acetylene with mercuric chloride:
ClCH=CHHgClC2 H2?HgCl 2
However, the investigations conducted by Nesmejanov and his collaborators demonstrated that β-chlorvinyl derivatives of heavy main group metals are actually organometallic compounds, containing multiple carbon-carbon bonds. Then in 1949 Nesmejanov offered a theory according to which dual reactivity of such compounds was due to σ,σ-conjugation between the carbon-mercury bond and carbon-chlorine bond, i.e. by the shift of electronic density of the following type:
From 1950 to 1959, Nesmejanov together with Nicolai K. Kochetkov conducted a series of experiments dedicated to the reactivity of βchlorvinylketones, which found application as convenient primary substances for the synthesis of aliphatic, aromatic, and heterocyclic compounds, particularly pyrazoles, pyrilium derivatives of pyridine salts, and so on. Furthermore, in these years Nesmejanov together with Rachel H. Freidlina studied reactions of polyhalogenated aliphatic compounds (particularly those containing the groups Cl3–CH2–, CCl3 CH=C< and CCl2=CH–, which enabled the development of new syntheses of compounds such as ω-chlorocarboxylic acids and αaminoacids.
Nesmejanov’s interest in synthesis of artificial foods developed primarily in the second half of 1950s and was connected with finding easier means of synthesizing α—aminoacids and α,α- dichloroalkenes of the type CCl2=CHR.
In the 1960s to 1970s, experiments with artificial foods became a key aspect of his work. The main problem he hoped to solve was to obtain food-grade protein without killing animals. The scientist stopped eating meat when he was nine years old, and at twelve he became a whole-hearted vegetarian, eliminating fish from his diet. He firmly believed in humane treatment of animals and not killing them. During the first stage of his experiments, he hoped to synthesize essential amino acids that one could add to broth and other dishes and later to develop peptides and then complete proteins.
Nesmejanov believed that it was possible to utilize heap food waste, such as casein from milk. As the experiments proceeded in full-gear, he said to his colleagues: “I think it’s worth starting with something that would stun society and break the wall of distrust around synthetic foods” (Slonimskii, 1999, p.10). When he was asked to clarify, he dreamily answered: “For example, start with caviar!” Indeed, in 1964, the Institute of Hetero-organic Compounds developed the first samples of artificial caviar from milk, and then they developed technology that obtained caviar from casein, protein and broken eggs, as well as other waste. His laboratory developed a synthetic black caviar that for a while was sold in Soviet grocery stores. Nesmejanov was very pleased with the results, but being a dedicated vegetarian, did not eat the caviar because it contained gelatin.
In the 1960s, Nesmejanov and his collaborators prepared ferrocerone, the first drug of the ferrocene series used to treat iron deficiency.
Administrative and Political Work Beginning in the 1940s, Nesmejanov spent progressively more time on administrative tasks. From 1945 to 1948 he served as dean of the Chemistry Faculty of Moscow University, and from 1948 to 1951 as the rector of the university. From his initiative stemmed construction of new buildings for the university in the Lenin (later Vorob’ev) Hills. After the creation of the Institute of Organic Chemistry in 1934, Nesmejanov ran the institute’s Laboratory of Organometallic Compounds, and in 1939 he was elected a corresponding member of the Academy of Science and president of the Institute of Organic Chemistry, over which he presided until 1954, when he organized an Institute of Hetero-organic Compounds. In 1943, he was elected an academician of the Academy of Sciences of the U.S.S.R., and from 1946 to 1948, he held the position of academician-secretary of the Department of Chemical Sciences of the Academy of Science. In 1951, Nesmejanov was appointed president of the Academy of Sciences of the U.S.S.R., in which post he served until 1961. During his presidency fifteen new institutes were created, including Institutes of Biological Physics (1952), Radio Technology and Electronics (1953), and Scientific Information (1952), the latter publishing a multiseries peer-reviewed journal (analogous to the American Chemical Abstracts) concerning all major branches of science. (In 1956, this institute was reorganized into the All-Union Institute of Scientific and Technological Information.) Besides these, numerous other institutes were created that focused on economic and sociopolitical as well as scientific topics.
As a president of the Academy of Sciences within a totalitarian system, Nesmejanov often ended up in difficult situations. For example, starting in 1946, a Soviet chemist, Gennadi V. Chelintsev, published papers, and in 1949 a book, in which he discussed his “new structural theory,” with which he challenged traditional “mechanistic” quantum chemistry. Nesmejanov strongly criticized Chelintsev’s ideas. This dispute revolved around the quantum chemical theory of resonance, proposed by Linus Pauling in 1930s, which was rejected by Chelintsev as contrary to Marxist dogma, but that was initially defended by Nesmejanov. In 1949 in No. 3 of the Soviet journal Voprosu philosophii [Problems of philosophy], two articles were published that were very critical of Pauling’s theory, one by Vladimir M. Tatevsky and Michael I. Shakhparonov, the other by Oleg A. Reutov. In both articles the theory of resonance was criticized only from an ideological standpoint. This theory was charged with “idealism” on the grounds that representing the same compound by several resonance structures violates the principle that each chemical compound should be represented by one formula. In 1949, a third article condemning Pauling’s theory appeared, and this time the author was Yuri A. Zhdanov (son of Joseph Stalin’s close friend, Andrey A. Zhdanov), who was then the head of the Science Department of the Central Committee of the Communist Party.
In 1950, Nesmejanov joined in criticism of the resonance theory. During a meeting of the Academic Council of the Institute of Organic Chemistry (February 1950), he called for further criticism of the theory and also made sure to challenge those instances in his own work that could have been interpreted as supportive of Pauling’s theory. This theory was proclaimed “physically baseless, and ideologically sinful” (1950, p. 442).
The campaign against the theory of resonance turned out to be absolutely fruitless both in scientific and administrative respects, unlike the campaign of 1948 against genetics when many people’s lives were destroyed by Lysenko. After the resonance case among chemists the biggest price was paid by Yakov K. Syrkin and Mirrah E. Dyatkina, who were fired from the Institute of Physical Chemistry, although rehired not too long after. Other “suspects” (Michael V. Vol’kenstein and Andrey I. Kirpianov) survived virtually unscathed, and Nesmejanov became the president of the Academy of Science in 1951. While the campaign against genetic studies led to annihilation of an entire branch of science in the USSR and to serious prosecution of scientists, the “anti-resonance” campaign on the other hand, touched on very specific theory and was nothing more than a superficial ritual that did not leave a deep imprint on the development of quantum chemistry in the Soviet Union, particularly because from the 1950s many chemists turned to the method of the molecular orbitals, which did not require the use of the theory of resonance.
At the same time Nesmejanov had a difficult relationship with Trofim D. Lysenko, who actively challenged genetics but was supported by the Soviet leaders Stalin and Nikita S. Khrushchev. Unlike the instance with the resonance theory, here Nesmejanov held his ground and refused to agree to any compromises supporting investigations on genetics in the USSR. “I listened to an entire course on genetics of the biology department in my student years,” he remembered, “and G. Mendel’s name in my mind stood next to that of John Dalton … I was too much of an optimist and was convinced that Lysenko and Lysenkoism would be an accidental and short-lived episode. I had no idea that this ‘episode’ would last thirty years” (1999, pp. 135–136.)
In April 1960, Khrushchev, under Lysenko’s influence, reproached Nesmejanov for certain supposed shortcomings of the Academy of Sciences, specifically the study of some “silly midges” (fruit flies). “I got up,” remembered Nesmejanov, “and to everyone’s horror, announced that the study of these very midges is of vital importance to many branches of science. That was an unheard of (public!) speech contradicting Khrushchev’s view. Then I said: ‘Undoubtedly, there is an option to replace the president [of the academy], to find an Academician more suitable for this role. I am convinced, for example, that Mstislav V. Keldysh would do much better with these tasks.’—‘I think so too,’ replied Khrushchev” (1999, p. 264). Shortly afterwards Nesmejanov was invited to the Kremlin where he was told that the leadership of the Communist Party had decided to appoint academician Mstislav V. Keldysh to the post. Nesmejanov had no choice but to resign.
Nesmejanov took his forced resignation from the post of president of the Academy of Science of U.S.S.R. rather lightly. The day after his resignation, almost all of the members of the academic council of the Institute of Hetero-organic Compounds, came over to his office to give him moral support. When he saw them at the door Nesmejanov asked in surprise: “What happened?” Then Martin I. Kabachnik said: “We gathered here to show solidarity, but do not know what to do next.” Nesmejanov smiled: “What to do? Let’s have a drink! After all I was reborn!” With that he went to the cupboard and got out a bottle of cognac and glasses. Having left a high post he was now able to dedicate himself to directing scientific experiments (primarily in the area of artificial foods) and to teaching.
Nesmejanov was awarded six Orders of Lenin (first in 1945, last in 1979), an Order of the Red Banner of Labor (1949), and a gold medal named for of M.V. Lomonosov (1961). He was a Laureate of the State (1943) and received the Lenin Prize of the U.S.S.R. (1966). At the direction of soviet leader Leonid I. Brezhnev, who held scientists in high respect (if they did not meddle in political matters as Andrei D. Sakharov did), the 1966 Lenin Prize and the 1979 Order of Lenin were given as sort of “rehabilitation” for his dismissal under Khrushchev. The spectrum of Nesmejanov’s interests was quite varied: he knew history well, wrote poems, and painted.
WORKS BY NESMEJANOV
“Eine neue Methode zur Synthese von aromatischen quecksilberorganischen Salzen.” Berichte der Deutschen Chemischen Gesellschaft 62 (1929): 1010–1018.
“Eine neue Methode zur Darstellung von symmetrischen aromatischen quecksilberorganischen Verbindungen.” Berichte der Deutschen Chemischen Gesellschaft 62 (1929): 1018–1020.
“über Doppelsalze von Phenyl-Diazoniumjodid mit Quecksilberjodid und über die Bildung von Diphenyljodoniumsalzen bei der Zersetzung dieser Doppelsalze.” Zeitschrift für Anorganische und Allgemeine Chemie 178 (1929): 300–308.
“Die Reaktion von quecksilberorganischen Verbindungen mit Salzen des zwei-wertigen Zinns als Methode zur Darstellung von zinnorganischen Verbindungen.” Berichte der Deutschen Chemischen Gesellschaft 63 (1930): 2496–2504.
“Aromatische Zinnverbindungen mit Halogen im Benzolkern.” Berichte der Deutschen Chemischen Gesellschaft 64 (1931): 628–636.
With E. I. Kan. “Di-β-Naphthyl Mercury.” Organic Syntheses 12 (1932): 46–47.
“β-Naphthylmercuric Chloride.” Organic Syntheses 12 (1932): 54–56.
“über die Synthese von quecksilber-organischen Verbindungen mit negativen Substituenten mittels der Diazo-Methode.” Berichte der Deutschen Chemischen Gesellschaft 67 (1934): 130–134.
“über die unmittelbare Synthese von S?ure-fluoriden aus S?uren und die Herstellung von Formylfluorid.” Berichte der Deutschen Chemischen Gesellschaft 67 (1934): 370–373.
“Carbonyls of the VI Group Metals in the Periodic System.” Comptes Rendus des Séances de l Académie des Sciences URSS 26, no. 1 (1940): 54–59. “Structure of Addition Products of Metal Halides and Unsaturated Compounds.” Comptes Rendus des Séances de l Académie des Sciences URSS 29, no. 8–9 (1940): 567–570.
With Rachel H. Freidlina. “Addition of Iodine Trichloride to Acetylene and the Structure of β-Chlorovinyl Iodochloride.” Doklady Akademii Nauk SSSR, Series A, 31, no. 9 (1941): 892–894.
“Otvet G.V. Chelintsevu” [Reply to G.V. Chelintsev]. Izvestiya Akademii nauk SSSR. Otdeleniye khimicheskikh nauk, no. 5 (1950): 544.
“O kontaktnukh khemicheskikh svyazakh i ‘novoy structurnoy teorii” [On “contact” chemical bonds and the “new structural theory”]. Izvestiya Akademii nauk SSSR. Otdeleniye khimicheskikh nauk, no. 2 (1952): 200.
“Réactivité double et tautomerie.” In XIVe Congrès international de chimie pure et appliquée: Conférences principales et conférences des sections. Zürich, 21.–27. VII. 1955. Basel: Birkh?user Verlag, 1955.
With Lubov’ G. Makarova and T. P. Tolstaya. “Heterolytic
Decomposition of Onium Compounds (Diphenylhalogenonium and Triphenyloxonium Salts).” Tetrahedron 1 (1957): 145–157.
“Die Anwendung der Telomerisationsreaktion zur Synthese von ω-Aminocarbons?uren und die Herstellung neuer Polyamidfasern auf ihren Basis.” Chemistry & Technology 9, no. 3 (1957): 139–150.
Izbrannuye trudu [Selected Works]. 4 vols. Edited by Aleksandr V. Topchiev. Moscow: Izdatel'stvo Akademii nauk SSSR, 1959.
Na kacheliakh XX veka [On a Swing of the Twentieth Century.] Moscow: Nauka, 1999.
Hunsberger I. M. “Theoretical Chemistry in Russia.” Journal of Chemical Education 31, no. 9-10 (1954): 504-514.
Kabachnik, Martin I., ed. Aleksandr Nikolaevich Nesmejamov: Uchenui i chelovek[Aleksandr Nikolaevich Nesmejanov: Scientist and Individual]. Moscow: Nauka, 1988.
Kursanov, D. M., M. G. Gonikberg, B. M. Dubinin, et al. “The Present State of Chemical Structural Theory.” Journal of Chemical Education 29, no. 1 (1952): 1-13.
Makarova, Lubov’ G. [no title]. In Aleksandr Nikolaevich Nesmejamov: Uchenui i chelovek [Aleksandr Nikolaevich Nesmejanov: Scientist and Individual], edited by Martin I. Kabachnik. Moscow: Nauka, 1988.
“Na uchenom sovete Instituta organichesloi khimii” [In Academic Council of the Institute of the Organic Chemistry]. Izvestiya Akademii nauk SSSR. Otdeleniye khimicheskikh nauk, no. 4 (1950): 438–444.
Reutov, O. A. “O knige G. V. Chelintseva ‘Ocherki po teorii organicheskoy khimii’” [On the Book by G.V. Chelintsev “Essays on the Theory of Organic Chemistry”]. Voprosu Filosofii[Problems of Philosophy] no. 3 (1949): 309–317/.
Slonimskii, Grigorii L. “Memoirs on Aleksandr Nesmejanov.” Khimia i jizn-XXI vek [Chemistry and Life—XXInd century], no. 9 (1999): 10.
Tatevskii V. M., and M. I. Shakhparonov. “About a Machistic Theory in Chemistry and its Propagandists.” Journal of Chemical Education 29, no. 1 (1952): 13-14.(Original publication: Tatevskii V. M., and M. I. Shakhparonov. “Ob odnoy makhistskoi teorii b eyo propadandistakh.” Voprosu Filosofii [Problems of Philosophy] no. 3 (1949): 176–192.
Tsupkin, Gennadii A., ed. Aleksandr Nikolaevich Nesmejanov: organizator nauki [Aleksandr Nikolaevich Nesmejanov: Manager of Science.] Moscow: Nauka, 1996.
Igor S. Dmitriev