The Laboratory of Organoaluminum and Organoboron Compounds was founded in May 1989. Its first chief was Professor Vladimir Bregadze, who headed the laboratory for more than 30 years - until January 2022, and since February 2022 the laboratory has been headed by Prof. Igor Sivaev. The research team includes 2 professors (Doctors of Chemical Sciences) and 7 doctors (Candidates of Chemical Sciences), graduate students and students. The main activity of the laboratory is the synthesis and study of the reactivity of derivatives of polyhedral boranes, carboranes and metallacarboranes.
Since 2001, the research team has published 325 experimental and review articles, 17 book chapters including Frontiers in Neutron Capture Therapy (2001), Boron Chemistry at the Beginning of the 21st Century (2002), Research and Development in Neutron Capture Therapy (2002), Boron Science: New Technologies and Applications (2012), Advances in Organometallic Chemistry and Catalysis (2014); Boron-Based Compounds: Potential and Emerging Applications in Medicine (2018), Handbook of Boron Science with Applications in Organometallics, Catalysis, Materials and Medicine (2019), Comprehensive Organometallic Chemistry IV (2022), Comprehensive Inorganic Chemistry III (2023) and 2 books (Polyhedral Boron Hydrides in Use: Current Status and Perspectives (2009) and Materials of modern electronics and spintronics (2018)). A number of researches have guest edited 7 special issues of European Journal of Inorganic Chemistry (2017), Journal of Organometallic Chemistry (2018), Molecules (2020, 2022, 2023), Inorganics (2023) and Crystals (2021), dedicated to the chemistry of boron compounds.
One of the most important achievements of the laboratory in the 21st century is the development of an effective method for the functionalization of anionic polyhedral boron hydrides through their cyclic oxonium derivatives. This method has no analogues in organic chemistry and is based on the reaction of polyhedral boron hydrides with cyclic ethers (tetrahydrofuran, 1,4-dioxane, tetrahydropyran) in the presence of non-nucleophilic Bronsted acids or Lewis acids, leading to the formation of cyclic oxonium derivatives, the stability of which is due to the strong electron-donor effect of the boron cage. The ring opening by nucleophilic attack leads to a wide variety of functional derivatives in which the functional group is separated from the boron cage by a flexible chain of 5-6 atoms, the hydrophobicity/ hydrophilicity of which depends on the cyclic ester taken.
This approach was originally proposed for the functionalization of the closo-dodecaborate anion [B12H12]2- (I. B. Sivaev, A. A. Semioshkin, B. Brellochs, S. Sjöberg, V. I. Bregadze. Polyhedron, 2000, 19, 627-632), and then extended to the closo-decaborate anion [B10H10]2- (A.V. Prikaznov et al., Polyhedron, 2011, 30, 1494-1501), cobalt bis(dicarbollide) [3,3'-Co(1,2-C2B9H11)2]- (I.B. Sivaev et al., J. Organomet. Chem., 2002, 649, 1-8), iron bis(dicarbollide) [3,3'-Fe(1,2-C2B9H11)2]- (I. Lobanova et al., Dalton Trans., 2015, 44, 1571-1584), 7,8-dicarba-nido-undecaborate anion [7,8-C2B9H12]- (M. Yu. Stogniy et al., Collect. Czech. Chem. Commun., 2007, 72, 1676-1688) and the 1-carba-closo-decaborate anion [1-CB9H10]- (A. V. Shmal'ko et al., Chem. Commun., 2022, 58, 3775-3778). Methods have been proposed for shortening the spacer formed during the opening of the 1,4-dioxane ring (A. V. Shmal'ko et al., Dalton Trans., 2015, 44, 9860-9871; J. Laskova et al., J. Organomet. Chem., 2017, 834, 64-72). This approach is particularly attractive for the preparation of boron-containing biologically active molecules and has been used for the synthesis of boron-containing amino acids, sugars, nucleosides, porphyrins, phthalocyanines, cholesterols, coumarins, acridines and other biomolecules. Eugene Nizhnik, Maria Berzina, Nadezhda Dudarova, Alexander Serdyukov, Olga Zhidkova, Dr. Julia Laskova, Dr. Marina Stogniy, Dr. Anna Druzina, Dr. Irina Lobanova, Dr. Irina Kosenko, Dr. Alexander Prikaznov, Dr. Akim Shmalko, Prof. Andrey Semioshkin, Prof. Igor Sivaev and Prof. Vladimir Bregadze participated in the work on the synthesis of various functional derivatives and boron-containing biomolecules based on cyclic oxonium derivatives of polyhedral boron hydrides at different times. Work in the field of synthesis and research of boron-containing biomolecules was carried out jointly with Zelinsky Institute of Organic Chemistry, Shemyakin and Ovchinnikov Institute of Bioorganic Chemistry, Lomonosov Moscow State University of Fine Chemical Technologies, Lomonosov Moscow State University, Institute of Medical Biology of the Polish Academy of Sciences, Indian Institute of Science Education and Research in Calcutta, Indian Center for Innovative Research, Southern Medical University in Guangzhou, University of Bremen and Istanbul Technical University.
The approach developed in the laboratory for the functionalization of anionic polyhedral boron hydrides through their cyclic oxonium derivatives is now widely used throughout the world and is a classical method for attaching closo-dodecaborate and cobalt bis(dicarbollide) moieties to various biomolecules. Various stages of development of this approach are reflected in review articles (A. A. Semioshkin, I. B. Sivaev, V. I. Bregadze, Dalton Trans., 2008, 977-992; I. B. Sivaev, V. I. Bregadze, Boron Science: New Technologies and Applications (Ed. N. S. Hosmane), CRC Press, 2012, 623-637; A. A. Druzina, A. V. Shmalko, I. B. Sivaev, V. I. Bregadze, Russian Chemical Reviews, 2021, 90, 785-830).
Another important area of research over the past 15 years has been the study of the influence of hydrogen bonds between dicarbollide ligands in derivatives of transition metal bis(dicarbollide) complexes [3,3'-M(1,2-C2B9H11)2]- (M = Co, Fe, Ni) on the conformation and properties of these complexes. These works started with the study of the influence of substituents in bis(dicarbollide) complexes on the crystal packing and electrical conductive properties of their radical cation salts with tetrathiafulvalenes (Dr. Irina Kosenko, Dr. Irina Lobanova) and ultimately led to the development of molecular switches based on bis(methylsulfide) derivatives [8,8'-(MeS)2-3,3'-M(1,2-C2B9H10)2]- (M = Co, Fe) (Dr. Sergey Anufriev). At various stages, work in this area was carried out jointly with the Institute of Problems of Chemical Physics, Perm State University, Karazin Kharkiv National University and Belozersky Research Institute of Physical and Chemical Biology.
In addition, the laboratory traditionally develops new methods for modifying ortho-carborane at carbon atoms (Dr. Marina Stogniy, Dr. Akim Shmalko, Dr. Sergey Anufriev) and boron (Dr. Sergey Anufriev, Dr. Akim Shmalko), as well as 7,8-dicarba-nido-undecaborate anion (nido-carborane) (Maria Zakharova, Olga Zhidkova, Dr. Sergey Anufriev, Dr. Sergey Timofeev, Dr. Akim Shmalko, Dr. Svetlana Erokhina, Dr. Marina Stogniy). In recent years, the laboratory has also been actively conducting work in the field of half-sandwiched metallacarboranes (Dmitry Semenov, Ekaterina Bogdanova, Dr. Svetlana Erokhina, Dr. Marina Stogniy, Candidate of Chemical Sciences M. Yu. Stogniy, Dr. Sergey Anufriev, Dr. Sergey Timofeev). Some of them are carried out in collaboration with Lobachevsky Nizhny Novgorod State University.
