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Development of organometallic chemistry on a joint of scientific schools of A.N.Nesmeyanov and G.A.Razuvaev

           


 

(The Lecture at the 100-th Birthday of Academician A.N.Nesmeyanov
at September, 9, 1999 in Nesmeyanov-Institute of Organoelement Compounds)
G.A.Domrachev
G.A.Razuvaev-Institute of Organometallic Chemistry, Russian Acad. Sci.,
49,Tropinin street, GSP-445, 603600, Russia;
Since the 1920’s there were friendly scientific contacts between A.N.Nesmeyanov and G.A.Razuvaev, which are now being maintained by their disciples
1920-30, N.D.Zelinsky 

Moscow  

State University & Acad.Sci. Institute of Organic Chemistry Institute of Organoelement Compounds (1954)  

  

  

Professor 

Academician 

The greatest organometallic school in Moscow and the USSR and Russia

1920-30, A.E.Favorsky 

Leningrad, V.N.Ipat'yev 

Technological Institute & Acad.Sci., High Pressure Lab. 

Gorky (Nizhny Novgorod) 

State University, Chem.Inst.  

Acad.Sci. Lab., Chem.Inst. 

Institute of Organometallic Chemistry 

Professor 

Academician 

The greatest organometallic school in Gorky and the second in the USSR and Russia 
 

The first works of both A.N.Nesmeyanov and G.A.Razuvaev were connected with the Kharasch's radical activity series.

 

Two series of organic radical activity by both: Nesmeyanov-Kocheshkov in polar elimination and Razuvaev in the radical substitution formed the theoretical basis of organometallic chemistry in the 1930’s.
 
 

 
In 1942 A.N.Nesmeyanov has evaluated a scientific contribution of Russian scientists into the organometallic chemistry development as following:

"The syntheses of organometallic compounds by exchange reaction of metals in organometallic compounds could be trivially represented as double exchange of salts or metal displacement. But this is not so, because of these reactions are not ionic. They proceed through free radical formation and their regularities are substantially different.

This group of reactions was a subject of wide researches (Nesmeyanov, 1930-42, Kocheshkov, 1930-1942, Razuvaev, 1928-1932)." [1]

 

 

[1] A.N.Nesmeyanov. The typical features of organic chemistry development in the USSR for 25 years. (The lecture has been made at the Anniversary Session of Chemistry Division of the USSR Academy of Sciences in November, 1942 in Sverdlovsk and Kazan).

Published in: Advances of Chemistry (Russ.). 12, 18 (1943).

In this review A.N.Nesmeyanov has cited 16 Razuvaev's publications in 2 references in spite of G.A.Razuvaev's name were stricktly forbidden because he was in a prison in the north. 

 

Nesmeyanov's formulations of stability problem of organometallic compounds [2] and their extension over wholly alkyls (homoleptic) of d and f elements [3] 

 

 

[2] A. N. Nesmeyanov, Advances of Chemistry (Russ.). 14, (4). 261 (1945).

[3] A. N. Nesmeyanov. Selected Works (Russ.). Moscow, USSR Acad. of Science, V. 2, p. 740, 1959.

have affected the development of sight on stability theory of organometallic compounds developed by G.A.Razuvayev's school (unaffected aspects of stability: quantum-chemical, thermodynamic. kinetic and synergetic [4-7] as well as the theory of hierarchies of structures [8] of organometallics and their solid decomposition products) [4]. G.A.Razuvaev, B.G.Gribov, G.A.Domrachev, B.A.Salamatin. Organometallics in Electronics. Moscow, Science, 1972 (in Russ.).

[5] B.G.Gribov, G.A.Domrachev, B.V.Zhuk, B.S.Kaverin, B.I.Kozyrkin, V.V.Mel'nikov, O.N.Suvorova. Deposition of films and coatings by decomposition of organometallics. Moscow, Science, 1981 (in Russ.).

[6] A.G.Razuvaev, G.A.Domrachev. Building the bonds in organometallics with high-symmetrical fragments. In book: Organometallics and Radicals. Moscow, Science, 1985, p.275-283.

[7] G.A.Domrachev, L.N.Zakharov, Yu.A.Shevelev. Russ.Chem.Revs. 54, (8), 739 (1985).

[8] G.A.Domrachev, A.I.Lazarev. Phys. Solid State. 41, (8). 720 (1999).

The development of chemistry of transition metal organic compounds in the USSR was starting by A.N.Nesmeyanov with studying the ferrocene chemistry [9] and by G.A.Razuvaev with preparation and research of bis-(arene)chromium derivatives [10]. [9] A.N.Nesmeyanov, E.G.Perevalova, R.V.Golovnya, O.A.Nesmeyanova. Substitution reactions of ferrocene hydrogens. Reports of the USSR Acad.Sci, 97, 459 (1954).

[10] G.A.Razuvaev, Yu.A.Sorokin, G.A.Domrachev. Photoreactions of organochromium compounds. Reports of the USSR Acad.Sci. 111, 1264 (l956).

The development of ferrocene chemistry at Nesmeyanov's school and that of bis-(arene)chromium at Razuvaev's school resulted in similar view on the reactivity:

 

"ricochet" reaction of polar substitution on reaction of ferricenium cation in the presence of ferrocene with hydrogen cyanide (Nesmeyanov [11]) and primary electrophilic attack on metal and following two competing reactions: hydrogen substitution and metal oxidation with electrophilic reagent (Domrachev, Sorokin [12]), which were experimentally confirmed and explained through the influence of space screening of metal by ligands (Domrachev, Zakharov [13]) exemplified by deuterium exchange in alkylferrocenes (Kochetkova, Lyatifov [14]) or by inhibition of metal oxidation on ferrocene alkylation with olefins in the presence of mixture À1Ñ1ç +LiAlH4 (Nesmeyanov, Kochetkova [15]) as well as by acylation of (h 6-benzene)-(h 5-cyclîpentadienyl)-rhenium (E.O.Fischer [16]).

[11] A.N.Nesmeyanov, E.G.Perevalova, L.P.Yur'yeva, L.N.Kakurina. Studying the reaction products of cyanation of methyl- and ethylferrocene. Chem.Bull. of the USSR Acad.Sci,1964, 1897.

[12] Yu.A.Sorokin, G.A.Domrachev. Some considerations on aromaticity of sandwich compounds of transition metals. On electrophilic substitution mechanism. Works on Chemistry and Chem.Technology, (Gor'ky), Nî. 3, 665 (1961).

[13] G.A.Domrachev, L.N.Zakharov, Yu.A.Shevelev. Russ.Chem.Revs. 54, 739 (1985).

[14] N.S.Kochetkova, I.R.Lyatifov

[15] A.N.Nesmeyanov, N.S.Kochetkova, S.V.Vitt, V.B.Bondarev, E.I.Kovshov. Reports of the USSR Acad.Sci., 156, 99 (1964).

[16] E.O.Fischer, JOM, (1986).

The comparison of reactivity of ferrocene and bis-(benzene)chromium(0) derivatives found in Nesmeyanov's and Razuvaev's school researches shows: 

In reactions with alkyl halides the main direction of ferrocene is an electrophilic substitution and as the side direction is an oxidation to ferricenium cation, which depends on a number of alkyl substituents in ferrocene [17].

 

 

[17] A.N.Nesmeyanov, N.S.Kochetkova, A.M.Vainberg, Yu.K.Krynkina. Chem.Bull. of the USSR Acad.Sci,1973, No.4, 945; Reports of the USSR Acad.Sci, 207, 808 (1972).

 

In reactions with alkyl halides the main direction of bis-(arene)chromium(0) is an oxidation to bis-(arene)chromium(I) cation [18].

[18] G.A.Razuvaev.G.A.Domrachev. Tetrahedron. 19, 341 (1963).

 

The stability of cations formed depends upon anion properties (covalent bond formation ability and charge transfer degree, delocalization of charge over many atoms, degree of space shielding) [4,19] [19] A.N.Nesmeyanov, L.P.Yur'yeva, R.B.Materikova, B.Ya.Getnarsky. Chem.Bull. of the USSR Acad.Sci.,1965, 731.
 
The decomposition of cation salts of Cp2Fe+l and (Arene)2Cr+1 derivatives proceeds through the similar mechanism of disproportionation to uncharged initial organometallic compound, derivative of two- or three-valent metal and organic products of decomposition (Cp2 or Arene) [4,5,20-26]

 

  

 

[20] R.A.Stukan, L.P.Yur'yeva. Reports of the USSR Acad.Sci, 167, 1311 (1966).

[21] B.G.Gribov, N.N.Travkin, G.M.Tabrina, V.P.Rumyantseva, B.A.Salamatin, B.I.Kozyrkin, A.S.Pashinkin. Ibid. 187, 330 (1969).

[22] O.N.Suvorova, G.A.Domrachev, G.A.Razuvaev. Ibid. 183, 850 (1968).

[23] G.A.Razuvaev, A.A.Koksharova, G.G.Petukhov, S.F.Zhil'tsov. Ibid. 187, 821 (1969).

[24] L.G.Abakumova. Sci. Notes of Gor'ky State Univ., Issue 105, 48 (1969).

[25] L.G.Abakumova, G.A.Abakumov, G.A.Domrachev. Reports of the USSR Acad.Sci., 197, 1315 (1971).

[26] G.A.Razuvaev, G.A.Domrachev, O.N.Suvorova, L.G.Abakumova. J.Organomet.Chem.32, 113 (1971).

The similarity of ferrocene and bis-(arene)chromium(0) was also shown in the reaction of b -cyanoethylation with nitrile of acrylic acid (AN).

 

 

 By Razuvaev's school studies the very high activity of bis-(arene)chromium(0), but not its cation, was shown. The violent exothermic reaction between components results in b -cyanoethylation of arenes bonded at Cr without oxidation of chromium(0) accompanied by intensive polymerization of AN with inclusion of oligomeric chains as substituents instead of hydrogen atoms of arenes [27,28]. This behavior is similar to reaction of phenols, but at the absence of a catalyst.

 

[27] G.A.Domrachev, G.A.Razuvaev. Interaction of dibenzenechromium(0) and acrylonitrile and mechanism of its polymerization. High-molecular compounds (Russ.), 4, No.l2, 1822 (1962).

[28] G.A.Domrachev, W.E.Douglas, B.Henner, L.G.Klapshina, V.V.Semenov, A.A.Sorokin. Bis(arene)chromium-containing polyacrylonitrile and its thermolysis products: synthesis, characterization and magnetic properties. Polymers for Advanced Technologies. 10, 215 (1999).

In Nesmeyanov's school work ferrocene was shown to react with acrylonitrile in the presence of two moles of aluminum chloride as a catalyst at elevated temperature [29,30] similarly to behavior of benzene. This reaction proceeds under hard conditions with limited yield of mono- and bis-b -cyanoethyl derivatives (25%) and recovering ferrocene (about 60% at reaction temperature 80°). [29] A.N.Nesmeyanov, M.I.Rybinskaya, G.B.Shul'pin. The cyanoethylation of ferrocene. Synthesis in Inorganic and Metallorganic Chemistry. 1, 279 (1971).

[30] A.N.Nesmeyanov, G.B.Shul'pin, A.A.Koridze, A.A.Pogrebnyak, M.I.Rybinskaya. Syntheses of l,l'-bis-(b -cyanovinyl) and l,l'-bis-(b -cyanoethyl)ferrocenes. Ibid. 3, 83 (1973).

These results indicate the higher activity of bis-(h 6-arene)chromium(0) in b -cyanoethylation as a reaction of electrophilic addition in comparison with ferrocene.

 

At the middle of seventies G.A.Razuvaev initiated the investigation of the direct cryosyntheses of organometallics of transition metals after Timms using high-vacuum cocondensation of metal vapor and organic compounds [31].

 

[31] G.A.Razuvaev, G.A.Domrachev, V.D.Zinov'yev. The direct synthesis of bis-(ethyl benzoate)chromium. Reports of the USSR Acad.Sci.223, 617 (1975). There was made the thermodynamic treatment of bis-(benzene)chromium [32] and ferrocene [33] direct-synthesis reaction and its relation to decomposition reaction. [32] G.A.Domrachev, V.D.Zinov'yev. J.Organomet.Chem., 117, 241 (1976).

[33] G.A.Domrachev, V.D.Zinov'yev. Chem.Bull. of the USSR Acad.Sci., 1976, 1429.

At the same time A.N.Nesmeyanov and his pupils (L.P.Yur'yeva, N.N.Zaitseva and others) have established a close contact with Razuvaev's synthetic group and have made some investigations on syntheses of exotic organometallics.

 

 

 The first example was bis-(benzene)chromium derivative of 1,4-diphenylbutane [34]. A.N.Nesmeyanov had a dream to synthesize any compound with a free metal atom inserted in a closed hollow hydrocarbon structure as "a bird in a cage". This paper was the first step to cyclophane derivatives of chromium containing two benzene connected by –(CH2)n- bridge. This compound was isolated besides with some dichromium compounds and polymers [34,35].

Other Cr-compounds [36].

 

[34] A.N.Nesmeyanov, N.N.Zaitseva, G.A.Domrachev, V.D.Zinov'yev, L.P.Yur'yeva, I.I.Tverdokhlebova. J.Organomet.Chem., 121, C52-C54 (1976).

[35] G.A.Domrachev, V.D.Zinov'yev, L.P.Yur'yeva, J.General Chem. (Russ.), 46, 2626 (1976).

[36] G.A.Domrachev, V.D.Zinov'yev, L.P.Yur'yeva, N.N.Zaitseva, One-step synthesis of bis-(arene)chromium complexes from ethyl esters of phenylacetic and phenylpropionic acids. Chem.Bull. of the USSR Acad.Sci., 1976, 1638.

 

 

 

Synthesis of bis-(diphenylphosphino-h 6-benzene)chromium from triphenylphosphine and chromium vapor [37].

 

 

 

[37] A.N.Nesmeyanov, L.P.Yur'yeva, N.N.Zaitseva, G.A.Domrachev, V.D.Zinov'yev, Yu.A.Shevelev, N.I.Vasyukova. Coordination Chem. (Russ.), 5, 673 (1979).

 

 

  

The low-temperature synthesis of ferrocenyl-substituted bis-(arene)chromium complexes [38].

 

 

[38] Yu.A.Shevelev, M.V.Dodonov, L.P.Yur'yeva, G.A.Domrachev, N.N.Zaitseva, Chem.Bull. of the USSR Acad.Sci., 1981, 1414.

 

. In spite of the very close contacts Nesmeyanov and Razuvaev published just one collaborative paper [39] on cryosynthesis of 1,1'-dialkylferrocenes from Featom and CpR, but there are some works by A.N.Nesmeyanov with Razuvaev's disciples in this area.

 

The single collaborative paper of A.N.Nesmeyanov and G.A.Razuvaev during their life was

"Direct syntheses of 1,1'-dialkylferrocenes with atomic iron"
 

 

[39] A.N.Nesmeyanov, G.A.Razuvaev, R.B.Materikova, G.A.Domrachev, V.D.Zinov'yev, N.P.Palitsyn, N.S.Kochetkova. J.General Chem. (Russ.), 48, 2132 (1978).

 

Nesmeyanov's ideas about synthesis of metal-inclusion compounds into a cage ("a bird in a cage") were unexpectedly realized
by synthesis of M@C60 and other metal-inserting fullerene derivatives in the 1990’s [40]; 

[40] N.Krawez, R.Tellgmann, I.V.Hertel, E.E.B.Campbell, A.Gromov, W.Kraetschmer. Collisions with fullerenes: from basic dynamics to the production and isolation of new materials. Mol.Mat., 10, 19-28 (1998) and references in it. as well as by Razuvaev's school works [4, 5,41,42] on the thermal decomposition of germanium tetraalkyls led to inserting Ge into carbon nanotubes. [41] G.A.Razuvaev, G.A.Domrachev, B.S.Kaverin, K.G.Kochetikhina (Shal'nova), B.A.Nesterov. Research of thermal decomposition of organogermanium compounds. Reports of the USSR Acad.Sci., 188, 607 (1969).

[42] P.I.Gromov, G.A.Domrachev, E.G.Domracheva, B.S.Kaverin. Formation of nanotubes on thermal decomposition of organogermanium compounds. Mol.Mat., 8, 5-12 (1996).

   Nesmeyanov's and Razuvaev's organometallic schools paid a great attention, besides of organometallic synthesis, also to the problems of stability and decomposition of organometallics, in particular, of transition metals. The latest results at Razuvaev's school closely related with research at Nesmeyanov's school are investigation of decomposition kinetics which were made earlier by Andreev and Dyagileva in collaboration with Nesmeyanov.

There are some collaborative papers of coworkers of both schools devoted to these problems initiated by A.N.Nesmeyanov and his works: 

[43] A.N.Nesmeyanov, G.I.Feklisov, B.Ya.Andreyev, L.M.Dyagileva, B.G.Andreyev. Thermal stability of tri-tert-butyl- and tetra-tert-butylferrocenes. Reports of the USSR Acad.Sci., 177, 859 (1967). – Decomposition kinetics of ferrocene and substituted ferrocenes is close to each other for all derivatives.

 

                [44] B.Ya.Andreyev, L.M.Dyagileva, G.I.Feklisov. Ibid., 158, 1348 (1964). – The similar kinetics of ferrocenes.

[45] L.M.Dyagileva. The investigation of kinetics and mechanism of thermal decomposition of ferrocenes. Ph.D.-Thesis, Gor'ky State Univ., 1971. –Ferrocene and its homologues obtained by N.S.Kochetkova and other coworkers of A.N.Nesmeyanov.

[46] B.V.Zhuk, N.M.Semenov, G.A.Domrachev. The role of adsorption in the decomposition process of 1,1'-diethylferrocene. J.General Chem. (Russ.). 48, 2562 (1978). – Adsorption of 1,1'-diethylferrocene on Al and Al2O3 surfaces and mechanism of decomposition.

[47] B.V.Zhuk, V.K.Khamylov, B.A.Nesterov, G.A.Domrachev, N.K.Zaglumonina. Influence of adsorbed ferrocene on morphology of pyrolytic films of aluminum Reports of the USSR Acad.Sci., 223, 862 (1977). – Change of the Al-crystal growth morphology on adsorption of ferrocene.

[48] B.V.Zhuk, G.A.Domrachev, N.M.Semenov, E.I.Mysov, R.B.Materikova, N.S.Kochetkova. The effect of the structure of alkylferrocenes on their fragmentation types upon electron impact. J.Organomet.Chem., 184, 231 (1980).

[49] Yu.A.Alexandrov, L.M.Dyagileva, E.I.Tsyganova. Thermal decomposition of organic derivatives of transition metals. M.: Sci.(1993).

Experimental investigation of heat capacities, combustion enthalpies and thermodynamic functions of acetyl- and 1,1'-diacetylferrocenes as well as liquid 1,1'-diethylferrocene, prepared in the laboratory of A.N.Nesmeyanov and theoretical evaluation by molecular dynamics of temperature dependence of total and potential energies of gas and condensed phases of these compounds were made in G.A.Razuvaev's school [50] (In the literature there are the only ferrocene thermodynamic data), as well as studies of quantum chemistry of Fe@C60-h 10 possible derivatives [51] (G. Domrachev, L. and E. Domracheva, G. Markin) and adduct of (h3-C5H5)2Ni with fullerene C60 [52] should be noted..(G.Domrachev, L. and E. Domracheva, G. Markin)

 [The latter ones are supported by RFFI (project N 96-15-97455) and RF Ministry of Sci. (project "Metal2" of the program "Fullerenes and atomic clusters"). 

 

 

[50] L.G.Domracheva, N.V.Karyakin, M.S.Sheiman, G.V.Kamelova, V.N.Larina, O.N.Suvorova, G.A.Domrachev. Thermodynamics and molecular dynamics of some ferrocene derivatives. Russian Chem. Bull. 1999, (9), 1647-1655 (Engl.),
 

 
              [51]                                                                              [52]
 

 

 

 

                 [51] E.G.Domracheva, L.G.Domracheva, G.V.Markin, G.A.Domrachev, A.M.Ob'yedkov. Proposal molecular and electronic structure of endo- and exo-iron complexes with fullerenes containing covalent polyhapto-bonds. 4th Biennial International Workshop in Russia "Fullerenes and Atomic Clusters", Book of Abstracts, IWFAC'99, October 4-8, 1999, St.Petersburg, Russia, p.57.

                [52] G.V.Markin, G.A.Domrachev, S.N.Titova, L.G.Domracheva, E.G.Domracheva. Molecular and electronic structure of nickelocene adduct with fullerene C60. School-Conference for Young Scientists "Organometallic Chemistry Towards the 21st Century", September 6-11, 1999, Abstracts of oral presentations and posters. Moscow, 1999, PY1.
 
 

Nesmeyanov's and Razuvaev's schools didn't pass by the unusual phenomena in chemistry, for example, nonlinear effects and oscillations.

There were discovered oscillatory reactions of

1) decomposition of organometallics on Chemical Vapor Deposition (heterogeneous gas-solid reaction) [4, 5, 53,54];

2) ligand exchange and decomposition of organometallics(Sn,Hg + Pd) in solution under limited diffusion conditions(effect of "Liesegang's rings") [55];

3) photochemical exciting–electron transfer oscillatory reaction between components of the system: (substituted ferrocene-alcohol-ferricenium cation) in solution [56].

 

[53] G.A.Domrachev, V.V.Mel'nikov, K.K.Fukin, G.A.Razuvaev. Reports of the USSR Acad.Sci., 184, 395 (1969). [Arene2Cr0 ® Cr+Cr7C3+C+CnHm+H2]

[54] B.V.Zhuk, V.K.Khamylov, B.S.Kaverin, G.A.Domrachev. Surface. Physics, Chemistry, Mechanics. 1982, (7) 112. [Et2Zn+H2Se® ZnSe,Zn,Se+EtH]

[55] G.V.Almazov, G.A.Domrachev, V.A.Varyukhin. I All-Union Conf. on Organomet.Chem., Abstr., Moscow: Sci., 1979, p.130. [Ph2Hg+AllPdCl® Pd+…]

[56] A.N.Nesmeyanov, N.S.Kochetkova, R.B.Materikova, I.R.Lyatifov, N.V.Fok, T.V.Burova, B.M.Yavorsky, V.N.Trembovler. Reports of the USSR Acad.Sci., 236, 624 (1977).

                             (  Cp2Fe+hn  ==> Cp2Fe*+EtOH  ==> Cp2Fe++(EtOH)·-  ==> Products     [56])