Theoretical Insight on the Formation Mechanism of a Trisubstituted Derivative of Closo-Decaborate Anion [B10H7O2CCH3(NCCH3)]0

Inorganics, Journal Year: 2023, Volume and Issue: 11(5), P. 201 - 201

Published: May 6, 2023

A theoretical modelling of the interaction process between a protonated complex carboxonium derivative [2,6-B10H8O2CCH3*Hfac]0 and acetonitrile molecule CH3CN was carried out. As result process, trisubstituted [B10H7O2CCH3(NCCH3)]0 formed. This reaction has an electrophile-induced nucleophilic substitution (EINS) mechanism. The main intermediates transition states were established. in case all previously investigated EINS processes, key intermediate anion with dihydrogen H2 fragment attached to one boron atom (B(H2) structure motif). can proceed on different position cluster cage. potential pathways assessed. It established that B4 cage most energetically favourable, [2,4,6-B10H7O2CCH3(NCCH3)]0 isomer

Language: Английский

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Synthesis of sandwich metallaboranes [M(B11H11)2]3– (M = Cu, Ag) via polyhedral expansion of the closo-undecaborate anion [B11H11]2–

Inorganica Chimica Acta, Journal Year: 2023, Volume and Issue: 556, P. 121675 - 121675

Published: July 5, 2023

Language: Английский

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Ionic conduction in ammonia functionalised closo-dodecaborates MB₁₂H₁₁NH₃ (M = Li and Na)

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(17), P. 7619 - 7627

Published: Jan. 1, 2024

Metal hydroborates offer impressive solid-state ion conduction, which may see them used in battery applications.

Language: Английский

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[closo-B₁₀H₈-10-PhI-1-COOH]⁻ Anion: An Intermediate for Functional Anionic Carboxylate Ligands

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(30), P. 13831 - 13834

Published: July 12, 2024

A potentially general intermediate, [closo-B10H8-10-PhI-1-COOH]–, for a class of functional anionic carboxylic acids, [closo-B10H8-10-X-1-COOH]2–, was obtained in four steps and 26% overall yield from [closo-B10H10]2–. It converted to the pyridinium derivative (X = C5H5N+) subsequently coordination complexes with (phen)2Cu2+ (phen)2Zn2+ ions. Both acid Zn(II) complex exhibit cage-to-pyridine charge-transfer band. The availability such acids opens access metal-ion compensated charges.

Language: Английский

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Photoelectron Spectroscopy and Computational Study on Microsolvated [B₁₀H₁₀]^2– Clusters and Comparisons to Their [B₁₂H₁₂]^2– Analogues

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(33), P. 6981 - 6988

Published: Aug. 7, 2024

Microhydrated closo-boranes have attracted great interest due to their superchaotropic activity related the well-known Hofmeister effect and important applications in biomedical battery fields. In this work, we report a combined negative ion photoelectron spectroscopy quantum chemical investigation on hydrated closo-decaborate clusters [B10H10]2–·nH2O (n = 1–7) with direct comparison analogues [B12H12]2–·nH2O free water clusters. A single H2O molecule is found be sufficient stabilize intrinsically unstable [B10H10]2– dianion. The first two molecules strongly interact solute forming B–H···H–O dihydrogen bonds while additional show substantially reduced binding energies. Unlike possessing highly structured network attached arranged unified pattern by maximizing bonding, distinct structural arrangements of within are achieved cluster networks from trimer heptamer resembling Such difference arises variations size, symmetry, charge distributions between these dianions. present finding again confirms diversity hydrogen-bonding microhydrated enriches our understanding aqueous borate chemistry.

Language: Английский

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Carboxonium Derivatives of closo-Decaborate Anion [2,6-B10H8O2CC6H4R]– Based on Aromatic Carboxylic Acids: Synthesis and Physicochemical Properties

Russian Journal of Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 15, 2024

Language: Английский

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Synthesis of Disubstituted Carboxonium Derivatives of Closo-Decaborate Anion [2,6-B10H8O2CC6H5]−: Theoretical and Experimental Study

Molecules, Journal Year: 2023, Volume and Issue: 28(4), P. 1757 - 1757

Published: Feb. 13, 2023

A comprehensive study focused on the preparation of disubstituted carboxonium derivatives closo-decaborate anion [2,6-B10H8O2CC6H5]− was carried out. The proposed synthesis target product based interaction between [B10H11]− and benzoic acid C6H5COOH. It shown that formation this proceeds stepwise through a mono-substituted [B10H9OC(OH)C6H5]−. In addition, an alternative one-step approach for obtaining derivative is postulated. structure tetrabutylammonium salts ((C4H9)4N)[2,6-B10H8O2CC6H5] established with help X-ray analysis. reaction pathway investigated density functional theory (DFT) calculations. This process has electrophile induced nucleophilic substitution (EINS) mechanism, intermediate anionic species play key role. Such intermediates have in which one boron atom coordinates two hydrogen atoms. regioselectivity 2,6-isomer also proved by theoretical Generally, experimental part, simple available producing introduced, mechanism can be applicable wide range closo-borate anions.

Language: Английский

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Synthesis and Structures of Lead(II) Complexes with Substituted Derivatives of the Closo-Decaborate Anion with a Pendant N3 Group

Molecules, Journal Year: 2023, Volume and Issue: 28(24), P. 8073 - 8073

Published: Dec. 13, 2023

In this work, we studied lead(II) and cobalt(II) complexation of derivatives [2-B10H9O(CH2)2O(CH2)2N3]2− [2-B10H9O(CH2)5N3]2− the closo-decaborate anion containing pendant azido groups in presence 1,10-phenanthroline 2,2′-bipyridyl. Mononuclear [PbL2{An}] binuclear [Pb2L4(NO3)2{An}] lead complexes (where {An} is N3-substituted boron cluster) were isolated by IR spectroscopy elemental analysis. The mononuclear complex [Pb(phen)2[B10H9O(CH2)2O(CH2)2N3] [Pb2(phen)4(NO3)2[B10H9O(CH2)5)N3] determined single-crystal X-ray diffraction. [Pb2(phen)4(NO3)2[B10H9O(CH2)5)N3], cluster coordinated metal atom only via 3c2e MHB bonds. [Pb(phen)2[B10H9O(CH2)2O(CH2)2N3], coordination environment includes BH oxygen exo-polyhedral substituent. When reaction was performed a CH3CN/water mixture, [(Pb(bipy)NO3)(Pb(bipy)2NO3)(B10H9O(CH2)2O(CH2)2N3)]·CH3CN·H2O isolated, where acts as bridging ligand between atoms cage O substituent and/or groups. course complexation, starting compound (Ph4P)2[B10H9O(CH2)5N3] its structure also Although number with N3 are known from literature, no group involved have been isolated.

Language: Английский

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One-Pot Synthesis of Heptanuclear Gold Cluster [Au7(Ph3P)7@C]2+ in the Presence of the Macropolyhedral Octadecahydroeicosaborate Anion [B20H18]2–

Russian Journal of Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 10, 2024

Language: Английский

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Playing with the Chaotropic Effect to Improve the Encapsulation of Decaborate Clusters within Cyclodextrins

Journal of Cluster Science, Journal Year: 2023, Volume and Issue: 35(1), P. 253 - 263

Published: July 25, 2023

Language: Английский

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