A combined ligand field and density functional theory study of the structural and spectroscopic properties of [Cu(dien)2]2+

Deeth, Robert J.

doi:10.1039/b008720n

Cited by 19 publications

(12 citation statements)

References 36 publications

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“…Alternatively, it has been proposed to use pure GGA functionals in combination with modified TM nuclear charge. Thus a reduction of nuclear charge by 0.8 for Cu(II) has lead to an excellent agreement with optical and ESR data for a wide range of Cu-amine complexes [15].…”

Section: Introductionsupporting

confidence: 63%

“…We intend to show that axial coordination and chemical environment are crucial in reproducing a correct ground state for these compounds. It is well known that DFT intrinsically overestimates TM-ligand covalency which becomes increasingly pronounced from left to the right of the TM series [14,15]. In this respect CuP is rather interesting.…”

Section: Introductionmentioning

confidence: 99%

“…To this end we adopted a recipe proposed by Deeth for Cu(II) amine complexes [15], which consists in taking a value of 28.2 for the nuclear charge of Cu(II) in order to reduce the metal-ligand covalency. The corresponding results are included in Fig.…”

Section: Ground State and Epr Spectra Of Cupmentioning

confidence: 99%

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A DFT based ligand field study of the EPR spectra of Co(II) and Cu(II) porphyrins

Atanasov

Daul

Rohmer

et al. 2006

Chemical Physics Letters

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. dedicate this work to the memory of late Prof. A. Schweiger. AbstractUsing a DFT based Ligand Field treatment (LFDFT) of the electronic structure of Co(II) and Cu(II) porphyrins (CoP and CuP) we analyse the origin of their EPR spectra. From a comparison between theoretical result on Co model clusters (CoP and CoP-ZnP dimer) we conclude that the g-tensor values are very sensitive to the axial coordination which stabilizes a 2 A 1 ground state in good agreement with experimental data. In contrast, DFT overestimates Cu-ligand covalency, leading to large discrepancy with experiments, and hence the orbital contribution to the computed g-values is too small. Using a numerical adjustment of nuclear charge for Cu, a good agreement between the computed and the experimental g-tensor values is observed. The influence of the DFT functional on the calculated g-tensor is also discussed.

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Section: Introductionsupporting

confidence: 63%

Section: Introductionmentioning

confidence: 99%

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A DFT based ligand field study of the EPR spectra of Co(II) and Cu(II) porphyrins

Atanasov

Daul

Rohmer

et al. 2006

Chemical Physics Letters

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“…The latter are also responsible for the splitting of the levels in a spin-unrestricted calculation when compared to the results of a spinrestricted one, as shown in Fig. 5 The electronic-transition energy estimated from the calculated molecular-orbital (MO) levels, based on one-electron excitations ending at the SOMO, differs strongly from the experimental results, as has been observed before for other Cu II complexes [27]. However, upon performing TD-DFT calculations with Gaussian98 [28], the mostintense UV/VIS bands were found to be at 684 and 512 nm, as compared to experimental values of 614 and 430 nm, respectively (see Table 1).…”

Section: IImentioning

confidence: 62%

“…This is a complementary approach to the classic ligand-field theory, which does neither directly include covalent bonds nor allow for mixing of d orbitals, when the symmetry is lowered from the octahedral group (O h ) [27]. Therefore, an attempt was made to predict the structure of [Cu II -2] 0 , as no crystal structure was available.…”

mentioning

confidence: 99%

Structure, Characterization, and Metal‐Complexation Properties of a New Tetraazamacrocycle Containing Two Phenolic Pendant Arms

Cui

Costa

Delgado

et al. 2004

Helvetica Chimica Acta

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The new tetraazamacrocycle 2 ( 2,2'- 7,11,.1]heptadeca-1(17),13,15-triene-3,11-diyl]bis(methylene)]bis(4-bromophenol)) was synthesized and used as a ligand for different metalion complexes. The X-ray crystal structures of the complexes of the general formula [M(H-2)] NO, in which only one of the two pendant phenolic OH groups of 2 is deprotonated, were determined. In both complexes, the coordination environment is of the [5 1] type, the four N-atoms of the macrocyclic framework defining a square-planar arrangement around the metal center, with similar NiÀN and ZnÀN distances of 1.961(9) to 2.157(9) ä and 2.021(9) to 2.284(8) ä, respectively. In contrast, the MÀO distances are markedly different, 2.060(6) and 2.449(8) ä in the Ni II complex, and 2.027(7) and 2.941(9) ä in the Zn II complex. The UV/VIS spectra of the Ni II and Cu II complexes with ligand 2, and the EPR spectra of the Cu II system, suggest the same type of structure for the complexes in solution as in the solid state. Theoretical studies by means of density functional theory (DFT) confirmed the experimental structures of the Ni II and Zn II complexes, and led to a proposal of a similar structure for the corresponding Cu II complex. The calculated EPR parameters for the latter and comparison with related data support this interpretation. The singly occupied molecular orbital (SOMO) in these systems is mainly made of a d orbital of Cu, with a strong antibonding (s*) contribution of the axially bound phenolate residue.

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Copper(II)‐Mediated Aromatic ortho‐Hydroxylation: A Hybrid DFT and Ab Initio Exploration

Comba

Knoppe

Martin

et al. 2007

Chemistry A European J

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Mechanistic pathways for the aromatic hydroxylation by [CuII(L1)(TMAO)(O)](-) (L1=hippuric acid, TMAO=trimethylamine N-oxide), derived from the O--N bond homolysis of its [CuII(L1)(TMAO)2] precursor, were explored by using hybrid density functional theory (B3LYP) and highly correlated ab initio methods (QCISD and CCSD). Published experimental studies suggest that the catalytic reaction is triggered by a terminal copper-oxo species, and a detailed study of electronic structures, bonding, and energetics of the corresponding electromers is presented. Two pathways, a stepwise and a concerted reaction, were considered for the hydroxylation process. The results reveal a clear preference for the concerted pathway, in which the terminal oxygen atom directly attacks the carbon atom of the benzene ring, leading to the ortho-selectively hydroxylated product. Solvent effects were probed by using the PCM and CPCM solvation models, and the PCM model was found to perform better in the present case. Excellent agreement between the experimental and computational results was found, in particular also for changes in reactivity with derivatives of L1.

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A combined ligand field and density functional theory study of the structural and spectroscopic properties of [Cu(dien)2]2+

Cited by 19 publications

References 36 publications

A DFT based ligand field study of the EPR spectra of Co(II) and Cu(II) porphyrins

A DFT based ligand field study of the EPR spectra of Co(II) and Cu(II) porphyrins

Structure, Characterization, and Metal‐Complexation Properties of a New Tetraazamacrocycle Containing Two Phenolic Pendant Arms

Copper(II)‐Mediated Aromatic ortho‐Hydroxylation: A Hybrid DFT and Ab Initio Exploration

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