DFT calculations of EPR parameters of transition metal complexes: Implications for catalysis

Saladino, Alexander C.; Larsen, Sarah C.

doi:10.1016/j.cattod.2005.04.018

Cited by 67 publications

(44 citation statements)

References 90 publications

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“…p y for N8). Finally, the calculated isotropic 13 C coupling constants with the (CN)eq groups perfectly agree with the measured value although the positive sign previously proposed for these couplings appears to be negative. Clearly, the good agreement between experimental and calculated parameters obtained for [Mo(CN) 5 NO] 3À shows that DFT calculations safely predict the structure of hexa-coordinated Mo(I) complexes; we will now use the DFT calculations on [Mo(CO) 5 PPh 3 ] + Á (Table 4) to identify the above-mentioned signals E (Table 1).…”

Section: [Mo(co) 5 Ph 3 ] + ásupporting

confidence: 82%

“…As reported by Hayes [14], one-electron oxidation of the Heide-Hofman cyanide leads to [Mo(CN) 5 NO] 3À , which could be incorporated in single crystals of K 3 Co(CN) 6 . Remarkably, this author could determine not only the g and Mo coupling tensors for this radical anion but he could also measure hyperfine interactions with the ligands: 14 N coupling tensors for NO and for the CN groups located in equatorial positions, as well as the 13 C isotropic coupling constant for these latter groups. As shown in Table 2, DFT calculations reproduce the main properties of the experimental g-tensor: axial symmetry, with g J $1.97 aligned along the Mo-NO bond direction, and g ?…”

Section: [Mo(co) 5 Ph 3 ] + ámentioning

confidence: 99%

“…Such investigations remain nevertheless rare and, probably due to their poor stability, radical cations formed from molybdenum pentacarbonyl derivatives are not known. This lack of experimental results can, of course, be overcome by using new methods of quantum chemistry to describe the electronic structure of such complexes [12,13]. It is clear, however, that the relevance of these calculations has to be checked by comparison with a well-established structure.…”

Section: Introductionmentioning

confidence: 99%

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Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

Sidorenkova

Berclaz

Ndiaye

et al. 2009

Journal of Physics and Chemistry of Solids

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a b s t r a c tA radical species characterized by a large g-anisotropy and a clearly resolved hyperfine structure with 95/97 Mo and 31 P nuclei is formed, at 77 K, by radiolysis of a single crystal of Mo(CO) 5 PPh 3 . The corresponding EPR signals disappear irreversibly with increasing temperature and the angular dependence of the various coupling constants imply a spin delocalization of $60% and $4% on the molybdenum and the phosphorus atoms, respectively and are, a priori, consistent with the trapping of a one-electron deficient centre. The ability of DFT to predict the EPR tensors for a 17-electron Mo (I) species is verified by calculating the g-tensor and the various 14 N and 13 C coupling tensors previously reported by Hayes for [Mo(CN) 5 NO] 3À . Calculations at the B3LYP/ZORA/SOMF level of theory show that, in contrast to Mo(CO) 5 PH 3 , one-electron oxidation of Mo(CO) 5 PPh 3 causes an appreciable change in the geometry of the complex. The g-tensor and the 95/97 Mo and 31 P isotropic and anisotropic coupling constants calculated for [Mo(CO) 5 PPh 3 ] + Á confirm the trapping of this species in the irradiated crystal of Mo(CO) 5 PPh 3 ; they also show that the conformational modifications induced by the electron release are probably hindered by the nearby complexes.

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Section: [Mo(co) 5 Ph 3 ] + ásupporting

confidence: 82%

Section: [Mo(co) 5 Ph 3 ] + ámentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

Sidorenkova

Berclaz

Ndiaye

et al. 2009

Journal of Physics and Chemistry of Solids

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“…So its ESR spectrum would give a large octet With comparable m n ratio, the unpaired electron was delocalized both on ligands and Ta (IV). (3) A ten of Ta (IV) was more than the bromo ligands.…”

Section: Prediction Of Number Of Esr Peaks In Ta (Iv) Complexesmentioning

confidence: 99%

“…Only a limited research work had been done in the experimental determination of number of ESR peaks in complexes of 4d and 5d metal ions [1][2][3][4][5] like Zr (III) [6][7][8] ,Hf (III) [7][8][9] ; Nb (IV) [10][11][12] , Ta (IV) 9 ; Tc (II) 9, 13, 14 , Re (II ) [15][16][17] ; Ru (III) [18][19][20][21][22][23][24] , Os (III) [18][19][20]24 ; Rh (IV) 25-27 , Ir (IV) 26,27 which formed five congeners of 2 nd and 3 rd transition series.…”

Section: Introductionmentioning

confidence: 99%

Predicting ESR Peaks in the 4d and 5d Transition Metal Ion Complexes by NMR, ESR and NQR Parameters: A DFT Study

Seghal¹,

Aggarwal²,

Kaul³

et al. 2017

Orient. J. Chem

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Computational chemistry was used to predict the number of ESR peaks in the 2 nd and 3 rd transition metal ion complexes by applying DFT implemented in ADF 2012.01.Only a limited experimental ESR research had been carried out in this field because high values of spin orbit coupling constants of these metal ions which provide an important energy transfer mechanism would adversely affect the values of ESR and NMR parameters (especially A ten ) of their complexes. Therefore, theoretical predictions were useful. ESR (A ten ) and NQR (NQCC,h) parameters of transition metal ions and the coordinating atoms of ligands were obtained from the ESR/EPR program while their shielding constants (s) and chemical shifts (d) were obtained from the NMR/EPR program after optimization of the complexes. Ligands whose coordinating atoms (CA) possessed the same values of the five parameters (A ten, NQCC, d,h, s) were expected to be spatially equivalent and would undergo the same hyperfine interaction with the central metal ion. 34 complexes of 10 metal ions consisting of five congeners: Zr (III), Hf (III) ; Nb (IV) ,Ta(IV) ; Tc (II), Re (II); Ru (III) ,Os(III) ;Rh (IV), Ir (IV) were selected to predict the number of ESR peaks.

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density functional theory

Frenking¹

2020

Catalysis From a to Z

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DFT calculations of EPR parameters of transition metal complexes: Implications for catalysis

Cited by 67 publications

References 90 publications

Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

Predicting ESR Peaks in the 4d and 5d Transition Metal Ion Complexes by NMR, ESR and NQR Parameters: A DFT Study

density functional theory

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