The isomers of α-amino-acids with copper(<scp>II</scp>). Part 5. The cis and trans isomers of bis(glycinato)copper(<scp>II</scp>), and their novel thermal isomerization

Delf, B. W.; Gillard, R. D.; O’Brien, Paul

doi:10.1039/dt9790001301

Cited by 48 publications

(33 citation statements)

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“…The conversion between the cis-and trans-[CuA C H T U N G T R E N N U N G (gly) 2 ] isomers can be rapidly realized in aqueous solution. [16] If Ln = La-Sm, the cis-[Cu- 6 Cu 24 ] nodes and give 3D 6. So, the rich variety of the Ln-Cu-glycine cluster compounds can be mainly attributed to the interselection between the dynamic control of metalloligands and the cationic components.…”

Section: Resultsmentioning

confidence: 99%

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Structural Diversity of Infinite 3d–4f Heterometallic Cluster Compounds Driven by Various Lanthanide Radii

Xiang

Sheng

et al. 2009

Chemistry A European J

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The syntheses, structures, and characterization of six Ln(3+)-Cu(2+)-glycine (Hgly) coordination polymers are described in this paper. They represent three types of structures. Type I (Ln=La (1), Pr (2), and Sm (3)) is a 1D catenarian polymer comprising [Ln(2)] nodes bridged by four cis-Cu(gly)(2) linkers. Type II (Ln=Eu (4) and Dy (5)) is a 2D open framework with a 4(4)-net, composed of novel [Ln(6)Cu(22)] cluster nodes linked by trans-Cu(gly)(2) linkers. Furthermore, the inner structures of the [Ln(6)Cu(22)] nodes, and the connection mode between the nodes and linkers are slightly different for 4 and 5. Type III (Ln=Er (6)) is a 3D open framework with a novel 3(6)4(18)5(3)6 topology, made up of [Er(6)Cu(24)] cluster nodes and trans-Cu(gly)(2) linkers. The rich variety of the resulting structures owes itself mainly to the interselection between the dynamic control of metalloligands and cationic components. A transition from frequency dependence to frequency independence is observed in the field-induced magnetization lag for 1-3. The frequency dependence at low temperatures may come from the antiferromagnetic Cu--Cu interaction through the [Ln(2)] nodes, whereas the frequency independence may be due to the disappearance of the antiferromagnetic Cu--Cu interaction at high temperatures.

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Section: Resultsmentioning

confidence: 99%

“…Crystal data for compound 3: C 16 (3), g = 94.53(3)8; V = 1483.5(5) 3 ; Z = 1; 1 calcd = 2.194 g cm À3 ; m = 3.751 mm À1 ; FA C H T U N G T R E N N U N G (000) = 966; GOF = 1.050. A total of 9968 reflections were collected, 5400 of which were unique (R int = 0.0218).…”

Section: Methodsmentioning

confidence: 99%

Structural Diversity of Infinite 3d–4f Heterometallic Cluster Compounds Driven by Various Lanthanide Radii

Xiang

Sheng

et al. 2009

Chemistry A European J

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“…Many copper(I1) bis(amino acid) complexes are known to exist in solution as a mixture of both isomers; they have slightly different tensors and g values, which contribute to the complexity of the nitrogen superhyperfine structure pattern (Goodman et al 1981, Goodman & McPhail 1985. Isomerization is probably very rapid for small complexes in solution since the energy barrier is low (Delf et al 1979), but this may not be the case for Cu-GSSG where the glutamyls are not free to move independently. Goodman and co-workers were able to detect cis and trans components of the high field peak in isotropic spectra of amino acid copper complexes, using isotopically pure CuZ+ in deuterated solvent (Goodman et al 1981, Goodman & McPhail 1985.…”

Section: Resultsmentioning

confidence: 99%

Copper-glutathione complexes under physiological conditions: structures in solution different from the solid state coordination

Steinkühler

Weser

et al. 1996

Biometals

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The physiologically important copper complexes of oxidized glutathione have been examined by electron spin resonance (ESR) spectroscopy in aqueous solution at neutral pH. Low temperature measurements show that the Cu(ll) binding site in oxidized glutathione has the same ligand arrangement as in the copper complexes of S-methylglutathione, glutamine, glutamate and glycine. The site is composed of the amino nitrogens and the carboxyl oxygens of two ?-glutamyl residues; there is no interaction with amide nitrogens, the sulphur bond or the glycyl carboxyl groups. At high metal to ligand ratios a binuclear species exists, in which each Cu(II) binds only to one 7-glutamyl residue. The previously reported forbidden transition detected at g = 4 is due to non-specific aggregation and not to spin coupling of intramolecular sites. Liquid solution ESR spectra show the Cu(II)-glutathione complex has a lower mobility than the corresponding Cu(II)-S-methylglutathione species. From the degree of spectral anisotropy the complex with glutathione is calculated to exist as a dimer. These results demonstrate that the physiologically relevant complex between copper and oxidized glutathione in solution is completely different from the known solid state structure determined by crystallography.

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“…A joint experimental and theoretical investigation of the inertness against racemization of cis-and trans-bis-(glycinato) copper(II) complexes [79] in aqueous solution marked the first application of the QMCF technique to a metal-organic system. While it was known for some time, that the associated crystals of those two isomers are stable and do not show racemization over time at temperatures below 180-210 °C [80], it was still an open question whether this is also true for the complexes in solution [81][82][83][84]. Figure 4 depicts the time series of the in-plane dihedral angle ϕ for cis-and trans-bis(glycynato) copper(II) in aqueous solution observed in the QMCF MD simulations at room temperature.…”

Section: Introductionmentioning

confidence: 98%

Perspectives for hybrid ab initio/molecular mechanical simulations of solutions: from complex chemistry to proton-transfer reactions and interfaces

Hofer

2014

Pure and Applied Chemistry

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As a consequence of the ongoing development of enhanced computational resources, theoretical chemistry has become an increasingly valuable field for the investigation of a variety of chemical systems. Simulations employing a hybrid quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) technique have been shown to be a particularly promising approach, whenever ultrafast (i.e., picosecond) dynamical properties are to be studied, which are in many cases difficult to access via experimental techniques. Details of the quantum mechanical charge field (QMCF) ansatz, an advanced QM/MM protocol, are discussed and simulation results for various systems ranging from simple ionic hydrates to solvated organic molecules and coordination complexes in solution are presented. A particularly challenging application is the description of proton-transfer reactions in chemical simulations, which is a prerequisite to study acidified and basic systems. The methodical requirements for a combination of the QMCF methodology with a dissociative potential model for the description of the solvent are discussed. Furthermore, the possible extension of QM/MM approaches to solid/liquid interfaces is outlined.

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The isomers of α-amino-acids with copper(II). Part 5. The cis and trans isomers of bis(glycinato)copper(II), and their novel thermal isomerization

Abstract: The Isomers of a-Amino-acids with Copper(i1). Part 5.V The cis and trans Isomers of Bis(glycinato)copper(ii), and their Novel Thermal lsomerization

Cited by 48 publications

References 0 publications

Structural Diversity of Infinite 3d–4f Heterometallic Cluster Compounds Driven by Various Lanthanide Radii

Structural Diversity of Infinite 3d–4f Heterometallic Cluster Compounds Driven by Various Lanthanide Radii

Copper-glutathione complexes under physiological conditions: structures in solution different from the solid state coordination

Perspectives for hybrid ab initio/molecular mechanical simulations of solutions: from complex chemistry to proton-transfer reactions and interfaces

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