Alkoxo-bridged binuclear copper(II) complexes as nodes in constructing extended structures

Tudor, Violeta; Marin, Geanina; Kravtsov, Victor Ch.; Simonov, Yurii A.; Lipkowski, Janusz; Brezeanu, M.; Andruh, Marius

doi:10.1016/s0020-1693(03)00241-x

Cited by 51 publications

(20 citation statements)

References 33 publications

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“…The Cu À O3A bond length of 1.9420 (14) does not differ from the standard values for m-O À Cu bonds and agrees with the lengths (ca. 1.91 À 1.95 ) found in related compounds, [35,40,41] whereas the Cu À O1 and Cu À O2 distances [2.5640(18) and 2.4445 (18) , respectively] are remarkably longer than the normal Cu À O amino alcohol bond distances. Nevertheless, they lie in the 2.43 -2.56 range reported for 2a, 5 [35] and other triethanolaminate complexes.…”

Section: X-ray Crystal Structures Of Complexes 1 and 2cmentioning

confidence: 92%

“…Nevertheless, they lie in the 2.43 -2.56 range reported for 2a, 5 [35] and other triethanolaminate complexes. [41,42] The Cu1 À O3 À Cu1A À O3A bridging mode is planar. The m-O3 atoms of the triethanolamine ligands generate a centrosymmetric Cu 2 O 2 core with an inversion centre disposed between the two copper atoms.…”

Section: X-ray Crystal Structures Of Complexes 1 and 2cmentioning

confidence: 99%

“…The Cu À Cu separation of 2.9222(5) and most of other bonding parameters agree with those found in related dinuclear complexes. [35,40,41] (1) …”

Section: X-ray Crystal Structures Of Complexes 1 and 2cmentioning

confidence: 99%

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Mild Peroxidative Oxidation of Cyclohexane Catalyzed by Mono‐, Di‐, Tri‐, Tetra‐ and Polynuclear Copper Triethanolamine Complexes

Kirillov¹,

Kopylovich²,

Kirillova³

et al. 2006

Adv Synth Catal

167

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Abstract:The mono-, di-, tri-, tetra-and polynuclear copper (II) (5), respectively, are highly active and selective catalysts or catalyst precursors for the peroxidative oxidation of cyclohexane, in acetonitrile, to a cyclohexanol and cyclohexanone mixture, by aqueous hydrogen peroxide in acidic medium (liquid biphasic catalysis) at room temperature and atmospheric pressure. The effects on the catalytic activity of various factors, e.g., the relative amounts of cyclohexane, oxidant, catalyst, solvent and nitric acid, reaction time, catalyst recycling and impact of both carbon-and oxygen-centred radical traps (supporting mainly radical mechanisms) were investigated and allowed us to achieve yields and TONs up to ca. 39% and 380, respectively, corresponding to the most active copper systems so far reported for the oxidation of cyclohexane under mild conditions. The catalysts can be reused for recycling and, at least complex 4 maintains almost the same level of activity even after five reaction cycles. The preparation of the new complexes 1, 2b and 2c by self-assembly at room temperature, and their full characterization by IR spectroscopy, FAB-MS þ , elemental and X-ray diffraction structural (for 1 and 2c) analyses are also reported.

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Section: X-ray Crystal Structures Of Complexes 1 and 2cmentioning

confidence: 92%

Section: X-ray Crystal Structures Of Complexes 1 and 2cmentioning

confidence: 99%

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Mild Peroxidative Oxidation of Cyclohexane Catalyzed by Mono‐, Di‐, Tri‐, Tetra‐ and Polynuclear Copper Triethanolamine Complexes

Kirillov¹,

Kopylovich²,

Kirillova³

et al. 2006

Adv Synth Catal

167

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“…The following types of cationic species have been used: 1) binuclear copper(ii) species with end-off compartmental Schiff base ligands, [9] 2) alkoxo-bridged copper(ii) species, [10] 3) heterobinuclear 3d-3d' species with macrocyclic compartmental ligands, [11] and 4) heterobinuclear 3d-4f species with side-off compartmental Schiff base ligands. [12] When the metal ions are different and paramagnetic, the intranode exchange interactions, as well as those between the resulting spins, may lead to interesting magnetic properties.…”

Section: Introductionmentioning

confidence: 99%

Oligonuclear 3d–4f Complexes as Tectons in Designing Supramolecular Solid‐State Architectures: Impact of the Nature of Linkers on the Structural Diversity

Gheorghe

Cucos

Andruh

et al. 2005

Chemistry A European J

Self Cite

268

105

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Heteronuclear cationic complexes, [LCuLn]3+ and [(LCu)2Ln]3+, were employed as nodes in designing high-nuclearity complexes and coordination polymers with a rich variety of network topologies (L is the dianion of the Schiff base resulting from the 2:1 condensation of 3-methoxysalycilaldehyde with 1,3-propanediamine). Two families of linkers have been chosen: the first consists of exo-dentate ligands bearing nitrogen-donor atoms (bipyridine (bipy), dicyanamido (dca)), whereas the second consists of exo-dentate ligands with oxygen-donor atoms (anions derived from the acetylenedicarboxylic (H2acdca), fumaric (H2fum), trimesic (H3trim), and oxalic (H2ox) acids). The ligands belonging to the first family prefer copper(II) ions, whereas the ligands from the second family interact preferentially with oxophilic rare-earth cations. The following complexes have been obtained and crystallographically characterized: [LCu(II)(OH2)Gd(III)(NO3)3] (1), [{LCu(II)Gd(III)(NO3)3}2(mu-4,4'-bipy)] (2), 1infinity[LCu(II)Gd(III)(acdca)(1.5)(H2O)2].13H2O (3), 2infinity[LCu(II)Gd(III)(fum)(1.5)(H2O)2].4H2O.C2H5OH (4), 1infinity[LCu(II)Sm(III)(H2O)(Hfum)(fum)] (5), 1infinity[LCu(II)Er(III)(H2O)2(fum)]NO3.3H2O (6), 2infinity[LCu(II)Sm(III)(fum)(1.5)(H2O)2].4H2O.C2H5OH (7), [{(LCu(II))2Sm(III)}2fum2](OH)2 (8), 1infinity[LCu(II)Gd(III)(trim)(H2O)2].H2O (9), 2infinity[{(LCu(II))2Pr(III)}(C2O4)(0.5)(dca)]dca.2H2O (10), [LCu(II)Gd(III)(ox)(H2O)3][Cr(III)(2,2'-bipy)(ox)2].9H2O (11), and [LCuGd(H2O)4{Cr(CN)6}].3H2O (12). Compound 1 is representative of the whole family of binuclear Cu(II)-Ln(III) complexes which have been used as precursors in constructing heteropolymetallic complexes. The rich variety of the resulting structures is due to several factors: 1) the nature of the donor atoms of the linkers, 2) the preference of the copper(II) ion for nitrogen atoms, 3) the oxophilicity of the lanthanides, 4) the degree of deprotonation of the polycarboxylic acids, 5) the various connectivity modes exhibited by the carboxylato groups, and 6) the stoichiometry of the final products, that is, the Cu(II)/Ln(III)/linker molar ratio. A unique cluster formed by 24 water molecules was found in crystal 11. In compounds 2, 3, 4, 9, and 11 the Cu(II)-Gd(III) exchange interaction was found to be ferromagnetic, with J values in the range of 3.53-8.96 cm(-1). Compound 12 represents a new example of a polynuclear complex containing three different paramagnetic ions. The intranode Cu(II)-Gd(III) ferromagnetic interaction is overwhelmed by the antiferromagnetic interactions occurring between the cyanobridged Gd(III) and Cr(III) ions.

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“…Fig.4a shows a projection down [001] where columnar voids along c can be clearly seen. This is precisely the locus of the perchlorate anions (Fig.4b) which dispose in these unoccupied regions, with weak interactions between themselves (Table 3, #4) and to the main frame (Table 3, #5 to #16) It is interesting to compare (I) with its related structure [Cu 2 (H 2 tea) 2 (dpe)]·2•(ClO 4 ) n• H 2 O (II), which is built up of exactly the same cationic 1D chains, but where the dimeric units in (I) are replaced by simple dpe spacers 1 . Charge balance is therein achieved by the presence of ordered perchlorate anions instead of the disordered ones in (I).…”

Section: Resultsmentioning

confidence: 99%

A Cu(II) POLYMERIC COMPLEX SURVEYING TRIETHANOLAMINE AND 1,2-DI(4-PYRIDYL)ETHYLENE AS BRIDGING LIGANDS

Atria

Parada

Garland

et al. 2015

J. Chil. Chem. Soc.

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Alkoxo-bridged binuclear copper(II) complexes as nodes in constructing extended structures

Cited by 51 publications

References 33 publications

Mild Peroxidative Oxidation of Cyclohexane Catalyzed by Mono‐, Di‐, Tri‐, Tetra‐ and Polynuclear Copper Triethanolamine Complexes

Mild Peroxidative Oxidation of Cyclohexane Catalyzed by Mono‐, Di‐, Tri‐, Tetra‐ and Polynuclear Copper Triethanolamine Complexes

Oligonuclear 3d–4f Complexes as Tectons in Designing Supramolecular Solid‐State Architectures: Impact of the Nature of Linkers on the Structural Diversity

A Cu(II) POLYMERIC COMPLEX SURVEYING TRIETHANOLAMINE AND 1,2-DI(4-PYRIDYL)ETHYLENE AS BRIDGING LIGANDS

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