Oleg Reutov

Scientific work

Oleg Alexandrovich Reutov was an outstanding chemist, he made a significant contribution to the development of organic, organometallic and physical organic chemistry.

In his laboratory (the laboratory of theoretical problems of organic chemistry), for the first time in the USSR, extensive investigations into the mechanisms of reactions of organometallic compounds were initiated, employing the most modern methods and concepts of physical chemistry.

The beginning of Reutov's scientific career was the continuation of the study of diazonium method, proposed by his scientific supervisor, A.N. Nesmeyanov. The method was aimed at obtaining some organometallic compounds, and Oleg Alexandrovich extended this method to the synthesis of organic derivatives of mercury, arsenic, antimony, and bismuth. He synthesized numerous novel double diazonium salts and conducted extensive research on mechanisms of these complex reactions. The logical continuation of his studies on diazonium salt chemistry led him into the field of onium compounds, particularly iodonium compounds. New methods for synthesizing mercury-, tin-, antimony-, and bismuth-organic compounds were developed. For the first time, salts of diaryliodonium with labeled iodine were synthesized.

Reutov was the first to insert mono- and dihalocarbenes (in particular, dichlorocarbene) across mercury-halogen bond, obtaining asymmetric mercury derivatives that contained a trichloromethyl group (R-Hg-Cl + :CCl2 = R-Hg-CCl3). Such substances long served as the best source of dichlorocarbenes and were termed "preserved carbenes".

Reutov was also one of the first to use labeled atoms to study the mechanisms of organic reactions, i.e. 203Hg was used to study exchange between metallic mercury and diarylmercury and 14C was used to investigate rearrangements in alkyl radicals.

An important part of Reutov's research work was a series of experiments conducted with many members of his laboratory on electrophilic substitution at saturated carbon atom. These works led to the discovery of a new mechanism of electrophilic substitution, SE1, wherein the rate-limiting step involves dissociation or ionization of an organometallic compound, followed by a rapid step in which the resulting carbanion or its ion pair interacts with an electrophilic agent. Subsequently, in the 1970s, intermediate cases between SE1 and SE2 mechanisms were identified – the ion-pair mechanism of bimolecular electrophilic substitution, in which ionization of the organometallic compound occurs in a pre-equilibrium step, followed by attack of the electrophilic agent on the ion pair in the rate-limiting step.

Based on polarographic data obtained by O. A. Reutov, a polarographic scale of acidity for CH-acids was constructed. This scale enabled characterization of CH-acids differing by nearly 60 pKa units and determination of the acidity of specific C–H bonds within molecules.

Parallel to his studies of electrophilic substitution reactions in organomercury compounds, Reutov discovered and investigated reactions proceeding by a homolytic mechanisms.

Reutov and his students conducted a series of studies on the mechanism of nucleophilic aromatic substitution and on anionic σ-complexes as possible intermediates in these reactions. They synthesized novel anionic σ-complexes of trinitrobenzene with C–E bonds in geminal positions (E = Si, Ge, Sn) and studied their transformation pathways in solution. A new rearrangement of these σ-complexes into 3,5-dinitrophenols was discovered.

A separate research cycle by O. A. Reutov was dedicated to the chemistry of arsenic and phosphorus ylides. Of particular interest was the synthesis of novel arsenic derivatives and the comparison of properties of arsenic and phosphorus ylides.

O. A. Reutov initiated a series of studies on the metal complexes, conducted using low-temperature NMR spectroscopy of heavy nuclei. Later, he investigated dynamic changes in metal complexes with unsaturated carbon-carbon bound and aromatic ligands.

Awards The list of awards is mainly taken from the book by T. Reutova. Order of the Red Star (May 17, 1944) Two Orders of the Patriotic War, 2nd Class (November 6, 1944; March 11, 1985) Order of the Patriotic War, 1st Class (June 3, 1945) Medal "For Victory over Germany in the Great Patriotic War 1941—1945" (1945) M. V. Lomonosov Prize, 1st Class (1956) – for the research cycle on the mechanism of synthesis of organometallic compounds via diazo compounds A. M. Butlerov Prize of the Presidium of the USSR Academy of Sciences (1961) – for a series of works in the field of organomercury compounds Two Order of the Red Banner of Labour (1961 – for outstanding contributions to training specialists and developing science; October 2, 1970 – for outstanding contributions to the development of chemical science, fruitful scientific and pedagogical activity, and in connection with his 50th birthday) Order of the October Revolution (September 17, 1975) – for contributions to the development of Soviet science and in connection with the 250th anniversary of the USSR Academy of Sciences Order of Lenin (September 4, 1980) – for outstanding contributions to the development of chemical science, training of scientific personnel, and in connection with his 60th birthday Lenin Prize (1984) – for the research cycle "Studies in the Field of Organometallic Chemistry of Non-transition Metals"