Design of Dinuclear Copper Species with Carboranylcarboxylate Ligands: Study of Their Steric and Electronic Effects

Fontanet, Mònica; Popescu, Adrian; Fontrodona, Xavier; Rodríguez, Montserrat; Romero, Isabel; Teixidor, Francesç; Viñas, Clara; Aliaga‐Alcalde, Núria; Ruiz, Eliseo

doi:10.1002/chem.201101929

Cited by 27 publications

(18 citation statements)

References 95 publications

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“…On the other hand, in previous works with carboranylcarboxylate ligands,14b we experimentally determined that electronic effects seemed to govern the reactivity toward the rupture of dinuclear Cu II structures, and the calculated CuX bond energies (X=N, O) confirmed the stronger interaction of the pyridylic ligands. All this led us to think that it would be possible to tune the degree of polymerization in our structures to obtain compounds with different nuclearity, if we chose an adequate ligand that could act as a stopper to close both ends of the polymers.…”

Section: Introductionsupporting

confidence: 48%

Water‐Soluble Manganese Inorganic Polymers: The Role of Carborane Clusters and Producing Large Structural Adjustments from Minor Molecular Changes

Fontanet

Rodríguez

Fontrodona

et al. 2014

Chemistry A European J

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The reaction of two different carboranylcarboxylate ligands, 1-CH3-2-CO2H-1,2-closo-C2B10H10 or 1-CO2H-1,2-closo-C2B10H11, with MnCO3 in water leads to polymeric compounds 1 a and 1 b. Both compounds have been characterized by analytical and spectroscopic techniques. Additionally, electrochemical techniques have also been used for compound 1 a. X-ray analysis revealed substantial differences between both compounds: whereas a six-coordinated Mn(II) compound with water molecules bridging two Mn(II) centers has been observed for 1 a, a square pyramidal geometry around each Mn(II) ion with terminal water molecules coordinated to each Mn(II) center has been found for 1 b. The observed differences have been attributed to the existence of different substituents, -CH3 or -H, on one of the carbon atoms of the carboranylcarboxylate ligand. The reaction of 1 a and 1 b with coordinating solvents, such as ethers or Lewis bases, leads to the formation of new compounds with low (mononuclear 4 a, 4 b; dinuclear 3 a, 3 b; and trinuclear 2 a) or high nuclearity (hybrid polymer, 5 a), due to breakage of the corresponding polymer. X-ray analysis shows that the structural core present in the polymeric materials is not maintained in the resulting compounds, with the exception of trinuclear compound 2 a. The magnetic properties of the compounds studied show weak antiferromagnetic coupling.

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Section: Introductionsupporting

confidence: 48%

Water‐Soluble Manganese Inorganic Polymers: The Role of Carborane Clusters and Producing Large Structural Adjustments from Minor Molecular Changes

Fontanet

Rodríguez

Fontrodona

et al. 2014

Chemistry A European J

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“…[42][43][44] Icosahedral boranes and carboranes ([B12H12] 2and 1,n-C2B10H12 (n = 2, 7 or 12) are a class of commercially available and exceptionally stable 3D-aromatic boron-rich clusters that possess material-favorable properties such as thermal and chemical stability and high hydrophobicity. 3,[45][46][47][48] The neutral carboranes are remarkably robust boron clusters with two carbon atoms and possess 26 electrons for 12 vertices.…”

Section: Introductionmentioning

confidence: 99%

A Highly Water-Stable meta-Carborane-Based Copper Metal–Organic Framework for Efficient High-Temperature Butanol Separation

et al. 2020

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Biofuels are considered sustainable and renewable alternatives to conventional fossil fuels. Biobutanol has recently emerged as an attractive option compared to bioethanol and biodiesel, but a significant challenge in its production lies in the separation stage. The current industrial process for the production of biobutanol includes the ABE (acetone−butanol−ethanol) fermentation process from biomass; the resulting fermentation broth has a butanol concentration of no more than 2 wt% (the rest is essentially water). Therefore, the development of a cost-effective process for separation of butanol from dilute aqueous solutions is highly desirable. The use of porous materials for the adsorptive separation of ABE mixtures is considered a highly promising route, as these materials can potentially have high affinities for alcohols and low affinities for water. To date, zeolites have been tested toward this separation, but their hydrophilic nature makes them highly incompetent for this application. The use of metal−organic frameworks (MOFs) is an apparent solution; however, their low hydrolytic stabilities hinder their implementation in this application. So far, a few nanoporous zeolitic imidazolate frameworks (ZIFs) have shown excellent potential for butanol separation due to their good hydrolytic and thermal stabilities. Herein, we present a novel, porous, and hydrophobic MOF based on copper ions and carborane−carboxylate ligands, mCB-MOF-1, for butanol recovery. mCB-MOF-1 exhibits excellent stability when immersed in organic solvents, water at 90 °C for at least two months, and acidic and basic aqueous solutions. We found that, like ZIF-8, mCB-MOF-1 is non-porous to water (type II isotherm), but it has higher affinity for ethanol, butanol, and acetone compared to ZIF-8, as suggested by the shape of the vapor isotherms at the crucial low-pressure region. This is reflected in the separation of a realistic ABE mixture in which mCB-MOF-1 recovers butanol more efficiently compared to ZIF-8 at 333 K.

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“…We have also reported the synthesis and characterization of copper complexes containing the carboranylcarboxylate ligand, L′ = [1-CO 2 -2-CH 3 -1,2-closo-C 2 B 10 H 10 ] − , along with their coordination chemistry and physical and chemical properties. 12 However, the coordination of Cu(II) to L = [1-CO 2 -2-H-1,2-closo-C 2 B 10 H 10 ] − is scarce, most probably due to the higher complexity in producing [1-CO 2 -2-H-1,2-closo-C 2 B 10 H 10 ] − than [1-CO 2 -2-CH 3 -1,2-closo-C 2 B 10 H 10 ] − , and due to the lack of awareness of the structural relevance of a -H vs. a -CH 3 . 13 With all this in mind, in this work we describe the reactivity of the dinuclear Cu II compound [Cu 2 (μ-L) 4 (THF) 2 ], 1, that contains the carboranylcarboxylate ligand L = 1-CO 2 H-2-H-1,2closo-C 2 B 10 H 10 and THF units as capping agents with different pyridyl ligands.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2015

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New dinuclear carboranylcarboxylate-bridged and mononuclear copper(ii) compounds containing the 1-CO2H-2-H-1,2-closo-C2B10H10 carborane ligand () have been synthesized from the previously synthesized dinuclear compound [Cu2(μ-L)4(THF)2], . Reaction of with CuSO4 in THF leads to the dinuclear compound [Cu2(μ-L)4(THF)2], . The reaction of with different terminal pyridyl ligands leads to the formation of a series of structurally analogous complexes by substitution of the terminal ligand THF (Lt = py, ; p-CF3-py, ; p-CH3-py, ), which maintain the structural Cu2(μ-O2CR)4 core in most of the cases except for o-(CH3)2-py where a mononuclear compound () is exclusively obtained. In the case of and , other dinuclear compounds [Cu2(L)4(Lt)4], and 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 and 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 is also discussed.

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Design of Dinuclear Copper Species with Carboranylcarboxylate Ligands: Study of Their Steric and Electronic Effects

Cited by 27 publications

References 95 publications

Water‐Soluble Manganese Inorganic Polymers: The Role of Carborane Clusters and Producing Large Structural Adjustments from Minor Molecular Changes

Water‐Soluble Manganese Inorganic Polymers: The Role of Carborane Clusters and Producing Large Structural Adjustments from Minor Molecular Changes

A Highly Water-Stable meta-Carborane-Based Copper Metal–Organic Framework for Efficient High-Temperature Butanol Separation

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

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