Boron cluster anions and their derivatives in complexation reactions

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 469, P. 214636 - 214636

Published: June 16, 2022

Language: Английский

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Physiologically Active Compounds Based on Membranotropic Cage Carriers–Derivatives of Adamantane and Polyhedral Boron Clusters (Review)

Russian Journal of Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 67(1), P. 28 - 47

Published: Jan. 1, 2022

Language: Английский

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B(9)-OH-o-Carboranes: Synthesis, Mechanism, and Property Exploration

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(13), P. 7331 - 7342

Published: March 24, 2023

Herein, we present a chemically robust and efficient synthesis route for B(9)-OH-o-carboranes by the oxidation of o-carboranes with commercially available 68% HNO3 under assistance trifluoromethanesulfonic acid (HOTf) hexafluoroisopropanol (HFIP). The reaction is highly wide scope carboranes, selectivity B(9)/B(8) up to 98:2. success this transformation relies on strong electrophilicity oxidizability HNO3, promoted through hydrogen bonds Brønsted HOTf solvent HFIP. Mechanism studies reveal that o-carborane involves an initial electrophilic attack atom at most electronegative B(9) o-carborane. In transformation, B-H bond nucleophilic site, which different from substitution reaction, where boron site. Therefore, oxidation-reduction mild conditions in N(V) → N(III) H(-I) H(I). derivatization 9-OH-o-carborane was further examined, carboranyl group successfully introduced amino acid, polyethylene glycol, biotin, deoxyuridine, saccharide. Undoubtedly, approach provides selective way rapid incorporation carborane moieties into small molecules application neutron capture therapy, requires targeted delivery boron-rich groups.

Language: Английский

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Effect of Nature of Substituents on Coordination Properties of Mono- and Disubstituted Derivatives of Boron Cluster Anions [BnHn]2– (n = 10, 12) and Carboranes with exo-Polyhedral B–X Bonds (X = N, O, S, Hal)

Inorganics, Journal Year: 2022, Volume and Issue: 10(12), P. 238 - 238

Published: Dec. 2, 2022

This review systematizes data on the coordination ability of mono- and disubstituted derivatives boron cluster anions carboranes in complexation with transition metals. Boron clusters [BnHn]2–, monocarborane [CBnHn–1]–, dicarboranes [C2BnHn–2] (with non-functionalized carbon atoms) (n = 10, 12) containing B–X exo-polyhedral bonds (X N, O, S, Hal) are discussed. Synthesis structural features complexes known to date described. The effect complexing metal substituent attached cage composition structures final is analyzed. It has been established that substituted can act as both ligands counterions. A agent coordinate due three-center two-electron 3c2e MHB bonds, by functional groups, or a mixed type be realized, through BH groups substituent. As for B-substituted carboranes, coordinated substituents salts non-coordinated carborane have isolated; compounds bonding not characteristic carboranes.

Language: Английский

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Variable Metal Chelation Modes and Activation Sequence in Pd-Catalyzed B–H Poly-arylation of Carboranes

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(22), P. 14047 - 14057

Published: Nov. 4, 2021

The development of synthetic methods for selective multiple functionalization B–H bonds offers great opportunity in expanding the application potentials carboranes. Herein, regioselective poly-arylation o-, m-, and p-carboranes has been developed by imine-directed, Pd-catalyzed iterative activation. isolation key palladium intermediates early stage late palladation validates distinct chelation-assisted modes at PdII center during activation pathways. In particular, a scarce three-coordinated, T-shaped complex isolated proven to be effective subsequent arylation reaction. Stoichiometric control on catalytic penta-arylation p-carborane led exhaustive mono-, di-, tri-, tetra-, penta-arylated products, which provides rationale that 5-fold proceeds sequence from vertex B(2) B(4), then B(5), finally B(3) B(6). It is steric factor introduced aryl groups affects performance metal selectivity chelation mode. A series cage B(3,4,5,6)-tetra-arylated o-carboranes B(2,3,4,5,6)-penta-arylated m- were synthesized good excellent yields as an unreported type molecular propellers. utility this method also illustrated.

Language: Английский

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Recent Achievements on Functionalization within closo‐Decahydrodecaborate [B₁₀H₁₀]²⁻ Clusters

ChemistrySelect, Journal Year: 2022, Volume and Issue: 7(21)

Published: June 1, 2022

Abstract Closo‐decahydrodecaborate anion, [B 10 H ] 2− , is one of the most notable clusters in family hydroborates, partly attributed to its unique electronic structure and thermal chemical stability. The major challenge development chemistry resides functionalization via activation exo‐polyhedral B−H bonds B−L generate attractive molecular construction modules or ‘archetypes’ useful applications. To date, closo‐[B cage has been functionalized with a wide range functional groups ‐L such as halogens, amines, thiols, alkoxy, hydroxyl multifunctional moieties yield mono‐ poly‐substituted borate derivatives. In this review, we present recent trends closo‐decaborate focus on substitution reactions hydrogen atoms by various entities.

Language: Английский

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Synthesis and Structures of Copper and Thallium(I) Coordination Compounds [Cu2[B10H10]]n and Tl2[B10H10] with the closo-Decaborate Anion

Russian Journal of Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 67(5), P. 628 - 635

Published: May 1, 2022

Abstract Solvent-free copper(I) and thallium(I) compounds of the general formula [M 2 [B 10 H ]] have been synthesized. The identified by IR spectroscopy X-ray diffraction. According to diffraction data, structures both are three-dimensional frameworks. In complex [Cu n , formation three-center M–H–B bonds is observed. compound Tl ], bond between cations anions ionic, which confirmed data. Hirschfeld surface analysis boron cluster anion was performed for identify analyze intramolecular interactions.

Language: Английский

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An Iridium-Stabilized Borenium Intermediate

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(40), P. 18359 - 18374

Published: Sept. 29, 2022

Exploration of new organometallic systems based on polyhedral boron clusters has the potential to solve challenging chemical problems such as stabilization reactive intermediates and transition-state-like species postulated for E-H (E = H, B, C, Si) bond activation reactions. We report facile clean B-H a hydroborane by iridium cluster complex. The product this reaction is an unprecedented fully characterized transition metal-stabilized cation or borenium. Moreover, intermediate bears unusual intramolecular B···H interaction between hydrogen originating from activated cyclometallated metal-bonded atom cluster. This proposed be arrested insertion into Bcage-metal initiation step "cage-walking" around upper surface process supported hydrogen-deuterium exchange observed at cluster, mechanism basis theoretical methods with special focus role noncovalent interactions. All compounds were isolated NMR spectroscopy elemental analysis. Key studied single crystal X-ray diffraction photoelectron spectroscopy.

Language: Английский

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Iron(II), cobalt(II), and nickel(II) complexes with 1,10-phenanthroline and 2,2′-bipyridyl and the macropolyhedral borane cluster [trans-B20H18]2- as counterion

Polyhedron, Journal Year: 2022, Volume and Issue: 217, P. 115740 - 115740

Published: Feb. 23, 2022

Language: Английский

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Luminescent cadmium(II) complexes with benzyl and chlorobenzyl benzimidazole derivatives and closo-decaborate anion

Inorganica Chimica Acta, Journal Year: 2023, Volume and Issue: 557, P. 121654 - 121654

Published: July 4, 2023

Language: Английский

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