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Intramolecular hydrogen bonding stabilizes the nuclearity of complexes. A comparative study based on the H-carborane and Me-carborane framework

New dinuclear carboranylcarboxylate-bridged and mononuclear copper(II) compounds containing the 1-CO2H-2-H-1,2-closo-C2B10H10 carborane ligand (LH) have been synthesized from the previously synthesized dinuclear compound [Cu-2(mu-L)(4)(THF)(2)], 1. Reaction of LH with CuSO4 in THF leads to the dinuclear compound [CCu2(mu-L)(4)(THF)(2)], 1. The reaction of 1 with different terminal pyridyl ligands leads to the formation of a series of structurally analogous complexes by substitution of the terminal ligand THF (L-t = py, 2; p-CF3-py, 3; p-CH3-py, 4), which maintain the structural Cu-2(mu-O2CR)(4) core in most of the cases except for o-(CH3)(2)-py where a mononuclear compound (5) is exclusively obtained. In the case of 2 and 4, other dinuclear compounds [Cu-2(L)(4)(L-t)(4)], 2’ and 4’ are obtained in lower yield. These compounds have been characterized using analytical, spectroscopic (NMR, IR, UV-visible) and electrochemical techniques (CV, DPV). X-ray analysis revealed a paddle-wheel structure for the main dinuclear compounds with a square-pyramidal geometry around each copper ion and the carboranylcarboxylate ions bridging two copper atoms in syn-syn mode. In the case of 2’ and 4’ there are two carboranylcarboxylate ions bridging the copper atoms in syn-anti mode whereas the other two adopt a monodentate coordination mode. The mononuclear complex obtained with the o-(CH3)-py ligand presents a square-planar structure, in which the carboranylcarboxylate ligand adoptsmonodentate coordination. The effect of the substituent group on the cluster of the carboranylcarboxylate ligands on the reactivity of compound 1 is also discussed

This research was financed by MEC of Spain through projects, CTQ2010-21532-C02-01, CTQ2013-44670-R, European Union (COST Action CM1302-Smart Inorganic Polymers) and the Generalitat de Catalunya (2014 SGR 149)

© Dalton Transactions, 2015, vol. 44, núm. 22, p. 10399-10409

Royal Society of Chemistry (RSC)

Manager: Ministerio de Ciencia e Innovación (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
Author: Fontanet, Mònica
Rodríguez Pizarro, Montserrat
Fontrodona, Xavier
Romero García, Isabel
Viñas, Clara
Teixidor Bombardó, Francesc
Date: 2015
Abstract: New dinuclear carboranylcarboxylate-bridged and mononuclear copper(II) compounds containing the 1-CO2H-2-H-1,2-closo-C2B10H10 carborane ligand (LH) have been synthesized from the previously synthesized dinuclear compound [Cu-2(mu-L)(4)(THF)(2)], 1. Reaction of LH with CuSO4 in THF leads to the dinuclear compound [CCu2(mu-L)(4)(THF)(2)], 1. The reaction of 1 with different terminal pyridyl ligands leads to the formation of a series of structurally analogous complexes by substitution of the terminal ligand THF (L-t = py, 2; p-CF3-py, 3; p-CH3-py, 4), which maintain the structural Cu-2(mu-O2CR)(4) core in most of the cases except for o-(CH3)(2)-py where a mononuclear compound (5) is exclusively obtained. In the case of 2 and 4, other dinuclear compounds [Cu-2(L)(4)(L-t)(4)], 2’ and 4’ are obtained in lower yield. These compounds have been characterized using analytical, spectroscopic (NMR, IR, UV-visible) and electrochemical techniques (CV, DPV). X-ray analysis revealed a paddle-wheel structure for the main dinuclear compounds with a square-pyramidal geometry around each copper ion and the carboranylcarboxylate ions bridging two copper atoms in syn-syn mode. In the case of 2’ and 4’ there are two carboranylcarboxylate ions bridging the copper atoms in syn-anti mode whereas the other two adopt a monodentate coordination mode. The mononuclear complex obtained with the o-(CH3)-py ligand presents a square-planar structure, in which the carboranylcarboxylate ligand adoptsmonodentate coordination. The effect of the substituent group on the cluster of the carboranylcarboxylate ligands on the reactivity of compound 1 is also discussed
This research was financed by MEC of Spain through projects, CTQ2010-21532-C02-01, CTQ2013-44670-R, European Union (COST Action CM1302-Smart Inorganic Polymers) and the Generalitat de Catalunya (2014 SGR 149)
Format: application/pdf
Citation: 023775
ISSN: 1477-9226 (versió paper)
1477-9234 (versió electrònica)
Document access: http://hdl.handle.net/10256/11710
Language: eng
Publisher: Royal Society of Chemistry (RSC)
Collection: MICINN/PN 2011-2014/CTQ2010-21532-C02-01
AGAUR/2014-2016/2014 SGR-149
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c5dt00305a
Articles publicats (D-Q)
Is part of: © Dalton Transactions, 2015, vol. 44, núm. 22, p. 10399-10409
Rights: Tots els drets reservats
Subject: Coure -- Compostos
Copper compounds
Enllaços d’hidrogen
Hydrogen bonding
Reaccions químiques
Chemical reactions
Title: Intramolecular hydrogen bonding stabilizes the nuclearity of complexes. A comparative study based on the H-carborane and Me-carborane framework
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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