What is the coordination number of copper(ii) in metallosupramolecular chemistry?

Chaurin, Valérie; Constable, Edwin C.; Housecroft, Catherine E.

doi:10.1039/b610306e

Cited by 51 publications

(37 citation statements)

References 58 publications

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“…A key step was to locate the low-energy conformers for each coordination number (4-6) and cluster size (n ) [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] hydrogen bond between water molecules on the periphery of a Cu(II)-water complex is stronger than the energy of water binding to the vacant axial sites on Cu 2+ . This much less favorable interaction of water molecules in the axial directions is due to the double occupation of the Cu 2+ 3d z 2 orbital effectively screening the positive charge on the metal ion.…”

Section: Discussionmentioning

confidence: 99%

“…Another direct consequence of the Jahn-Teller effect is the flexibility (plasticity) of the coordination geometry of Cu(II) which can adopt a variety of coordination geometries in the crystalline phase. [6][7][8][9][10][11][12][13] For example, crystal structures of Cu(II)-amino acids complexes with four-, five-, and six-coordinate geometries are all common, suggesting that energetic differences between them are small. Consistent with the Jahn-Teller effect, many of these structures include irregular or distorted coordination geometries.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][4][5] Detailed information on ligands arrangement around the Cu(II) ion is only available in the solid state [6][7][8][9][10][11][12][13] whereas the structural information in the aqueous phase [13][14][15][16][17][18][19][20] is less definitive and available only for few Cu 2+ complexes. Although static [20][21][22][23][24][25][26][27][28][29][30] and dynamic [31][32][33][34][35][36][37] electronic structure calculations can, in principle, provide such information, realistic modeling of Cu(II) complexes in aqueous solution with highly flexible coordination environment still remains a challenge.…”

Section: Introductionmentioning

confidence: 99%

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Hydration of Copper(II): New Insights from Density Functional Theory and the COSMO Solvation Model

et al. 2008

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The hydrated structure of the Cu(II) ion has been a subject of ongoing debate in the literature. In this article, we use density functional theory (B3LYP) and the COSMO continuum solvent model to characterize the structure and stability of [Cu(H 2 2+ clusters as a function of coordination number (4, 5, and 6) and cluster size (n ) 4-18). We find that the most thermodynamically favored Cu(II) complexes in the gas phase have a very open four-coordinate structure. They are formed from a stable square-planar [Cu(H 2 O) 8 ] 2+ core stabilized by an unpaired electron in the Cu(II) ion d x 2 -y 2 orbital. This is consistent with cluster geometries suggested by recent mass-spectrometric experiments. In the aqueous phase, we find that the more compact five-coordinate square-pyramidal geometry is more stable than either the four-coordinate or six-coordinate clusters in agreement with recent combined EXAFS and XANES studies of aqueous solutions of Cu(II). However, a small energetic difference (∼1.4 kcal/mol) between the five-and six-coordinate models with two full hydration shells around the metal ion suggests that both forms may coexist in solution.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Hydration of Copper(II): New Insights from Density Functional Theory and the COSMO Solvation Model

et al. 2008

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“…Distortion of the octahedral geometry occurs along one of the three 4-fold axes. One of the important consequences of the Jahn-Teller effect is a variability of the coordination geometry of Cu 2+ in the solid state [14][15][16][17][18][19][20][21] and the fast first-shell ligand exchange dynamics in the aqueous phase. 22,23 Surprisingly, the coordination environment even for the simplest hydrated Cu(II) ion has been the subject of extensive debate in recent years.…”

Section: Introductionmentioning

confidence: 99%

Computational Study of Copper(II) Complexation and Hydrolysis in Aqueous Solutions Using Mixed Cluster/Continuum Models

2009

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We use density functional theory (B3LYP) and the COSMO continuum solvent model to characterize the structure and stability of the hydrated Cu(II) complexes [Cu(MeNH 2 2-x (x ) 1-3) as a function of metal coordination number (4-6) and cluster size (n ) 4-8, 18). The small clusters with n ) 4-8 are found to be the most stable in the nearly square-planar four-coordinate configuration,, which is three-coordinate. In the presence of the two full hydration shells (n ) 18), however, the five-coordinate square-pyramidal geometry is the most favorable for Cu (MeNH 2 ) 2+ (5, 6) and Cu(OH) + (5, 4, 6), and the four-coordinate geometry is the most stable for Cu(OH) 2 (4, 5) and Cu(OH) 3 -(4). (Other possible coordination numbers for these complexes in the aqueous phase are shown in parentheses.) A small energetic difference between these structures (0.23-2.65 kcal/mol) suggests that complexes with different coordination numbers may coexist in solution. Using two full hydration shells around the Cu 2+ ion (18 ligands) gives Gibbs free energies of aqueous reactions that are in excellent agreement with experiment. The mean unsigned error is 0.7 kcal/mol for the three consecutive hydrolysis steps of Cu 2+ and the complexation of Cu 2+ with methylamine. Conversely, calculations for the complexes with only one coordination shell (four equatorial ligands) lead to a mean unsigned error that is >6.0 kcal/mol. Thus, the explicit treatment of the first and the second shells is critical for the accurate prediction of structural and thermodynamic properties of Cu(II) species in aqueous solution.

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“…A search of the Cambridge Structural Database (Conquest v. 5.30 with September 2009 updates, [17]) revealed that no other complexes containing ligand 2 have been structurally characterized, even though the coordination chemistry of the parent ligand 1 is well documented [1,2]. Given the stability associated with {Cu(tpy) (bpy)} 2+ coordination environments [18,19], we decided to investigate the one-pot reactions of copper(II) ions, tpy and ligand 2.…”

mentioning

confidence: 99%

Capturing copper(II) ions using {Cu(tpy)(bpy)} domains

Constable

Housecroft

Price

et al. 2010

Inorganic Chemistry Communications

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What is the coordination number of copper(ii) in metallosupramolecular chemistry?

Cited by 51 publications

References 58 publications

Hydration of Copper(II): New Insights from Density Functional Theory and the COSMO Solvation Model

Hydration of Copper(II): New Insights from Density Functional Theory and the COSMO Solvation Model

Computational Study of Copper(II) Complexation and Hydrolysis in Aqueous Solutions Using Mixed Cluster/Continuum Models

Capturing copper(II) ions using {Cu(tpy)(bpy)} domains

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