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Polyhedral Boranes and Carboranes
Ch. 9.05. P. 196–262.
Igor B. Sivaev
In book
Vol. 9. , Elsevier, 2022.
Ankudinov N., Alexeev N., Podyacheva E. et al., Chemical Science 2025 Vol. 16 No. 15 P. 6298–6306
Organic compounds with boron–nitrogen bonds are widely used as fluorescent sensors and semiconducting materials. This paper presents a new approach for the formation of B–N bonds via catalytic insertion of nitrenes into B–H bonds. The reaction proceeds most selectively for cyclic boranes with a 2-phenylpyridine framework and nitrenes generated in situ by the oxidation of ...
Added: February 15, 2026
Ankudinov N., Komarova A., Evgeniya S. Podyacheva et al., Chemical Communications 2024 Vol. 60 No. 65 P. 8601–8604
Molecules with chiral boron atoms have been scarcely studied due to limited synthetic access. Herein, we report a new method for their synthesis via asymmetric insertion of arydiazoacetates into the B–H bonds of prochiral carbene–boranes NHC–BH2R. The reaction is catalyzed by the rhodium(I) complex with the chiral diene ligand
tBu2-TFB, which can be conveniently prepared by ...
Added: February 23, 2025
Timofeev S., Kirill E. Erdelyi, Suponitsky K. et al., Journal of Organometallic Chemistry 2023 Vol. 1002 Article 122906
Complexation of B-closo- and nido-carboranyl methyl thioethers with the pentacarbonyltungsten fragment was studied. An unusual instability of the nido-derivative is detected and rationalized by means of the quantum chemical calculations followed by the topological analysis of electron density and the Interacting Quantum Atoms analysis. The structure of {(CO)5W[9-MeS-1,2-C2B10H11-κ1-S(1)]} was determined by single crystal X-ray diffraction. ...
Added: June 24, 2024
Sivaev I., , in: Comprehensive Inorganic Chemistry IIIVol. 1.: Elsevier, 2023.
This chapter describes recent progress in the chemistry of molecular boron clusters. The greatest attention is paid to the
intensively developing chemistry of closo-decaborate [B10H10]2- and closo-dodecaborate [B12H12]2- anions. Of the
compounds with an open nido- and arachno-structures, the latest achievements in the chemistry of decaborane [B10H14] and macropolyhedral borane anti-[B18H22] attract the most attention. ...
Added: October 26, 2023
Semyonov, D., Slushko G., Stogniy M. et al., Organometallics 2023 Vol. 42 No. 18 P. 2522–2530
Reactions of nickel(II) phosphine complexes [(dppe)NiCl2], [(MePh2P)2NiCl2] and [(Ph3P)2NiCl2] with C-substituted nido-carboranes [7-R-nido-7,8-C2B9H11]− (R = Me, Ph, C(NHCy)2+) were studied. The reactions with [(dppe)NiCl2] lead to the corresponding nickelacarboranes 3,3-(dppe)-1-R-closo-3,1,2-NiC2B9H10 with absent or negligible steric interactions between the ligands. The reactions of [(MePh2P)2NiCl2] with [7-R-nido-7,8-C2B9H11]− (R = H, Me, Ph) result in nickelacarboranes 3,3-(MePh2P)2-1-R-closo-3,1,2-NiC2B9H10 with noticeable steric loading, while the reaction ...
Added: October 25, 2023
Igor B. Sivaev, Anufriev S., Shmalko A., Inorganica Chimica Acta 2023 Vol. 547 Article 121339
Based on the data of 1H NMR spectra, the effect of various substituents at boron atoms in different positions of the ortho-carborane cage on its CH-acidity and the electron-withdrawing effect upon substitution at the carbon atom is considered. The introduction of chlorine atoms to the boron atoms opposite to the carbon atoms (positions 9 and 12) slightly reduces ...
Added: January 29, 2023
Shmal’ko A., Cendoya P., Anufriev S. et al., Chemical Communications 2022 Vol. 58 No. 23 P. 3775–3778
Two new approaches to the functionalization of the 1-carba-closodecaborate anion [1-CB9H10] at boron atoms via the ring-opening of its 1,4-dioxane derivative with various nucleophiles and Pd-catalysed cross-coupling of its iodo derivative with aromatic amines and heteroaromatics were developed. ...
Added: January 29, 2023
Stogniy M., Anufriev S., Shmal’ko A. et al., Dalton Transactions 2021 Vol. 50 No. 7 P. 2671–2688
An unusual reactivity of 9-iodo-nido-carborane [9-I-7,8-C2B9H11]− towards nucleophiles under strong basic conditions was revealed. The nucleophilic substitution of iodine with O- and N-nucleophiles results in [9-RO-7,8-C2B9H11]− (R = H, CH2CH2OMe) and [9-L-7,8-C2B9H11] (L = Py, NEt3, Me2NCH2CH2NMe2), respectively. Reaction of [9-I-7,8-C2B9H11]− with CoCl2 in 1,2-dimethoxyethane in the presence of t-BuOK, depending on the order of addition of the reagents, ...
Added: April 17, 2022
Sivaev I., Stogniy M., Bregadze V., Coordination Chemistry Reviews 2021 Vol. 436 Article 213795
Synthesis and structure of transition metal complexes with phosphine ligands derived from icosahedral dicarbaboranes C2B10H12, monocarbaboranes [CB9H10]- and [CB11H12]-, as well as various metallacarboranes are reviewed. Possibilities of practical application of such complexes are discussed. ...
Added: April 8, 2022