Multinuclear, multifield, and multiphase nuclear magnetic resonance study of cadmium meso-tetraphenylporphyrin and its pyridine adduct

Jakobsen, Hans J.; Ellis, Paul D.; Inners, Ruth R.; Jensen, Claus F.

doi:10.1021/ja00390a010

Cited by 62 publications

(55 citation statements)

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“…3 Similarly, Jakobsen et al solid-state NMR experiments identified the compensatory effect of two tensor elements in mesotetraphenylporphyrin and its pyridyl adduct, which led to a small chemical shift difference of 33 ppm. 4 To further understand the chemical principles underlying the variation of the 113 Cd CSA tensor, solid-state NMR experiments can be supplemented with ab initio calculations. In this paper, we present quantum chemical approaches to calculate the 113 Cd CSA tensors that can be directly compared with the experimental data for further applications.…”

Section: Introductionmentioning

confidence: 99%

Quantum Chemical Calculations of Cadmium Chemical Shifts in Inorganic Complexes

Kidambi

Ramamoorthy

2002

J. Phys. Chem. A

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This study reports a systematic approach of ab initio calculations of 113 Cd chemical shifts to understand the coordination chemistry of cadmium complexes. Cadmium-113 chemical shifts were calculated using HartreeFock (HF) and density functional theoretical (DFT) methods for cadmium complexes, dimethylcadmium (CdMe 2 ), diethylcadmium (CdEt 2 ), methylethylcadmium (CdMeEt), cadmium nitrate tetrahydrate [Cd(NO 3 ) 2 ‚ 4H 2 O], and cadmium acetate dihydrate [Cd(OAc) 2 ‚2H 2 O]. Theoretical and experimental chemical shift values are compared in order to determine the effectiveness of theoretical calculations in determining cadmium chemical shifts. We also determined the magnitude of the principal elements of the 113 Cd CSA tensor values for hydrated cadmium nitrate and cadmium acetate. The effect of different cadmium basis sets such as polarized double-split valence, 3-21G, and uncontracted Sadlej on chemical shift values was also evaluated. The density functional calculations were found to match the experimental chemical shift values considerably better than the Hartree-Fock calculations. Further, the agreement between the theoretical and experimental values significantly improved with the inclusion of a sufficient number of water molecules. Cadmium-113 chemical shifts of several cadmium complexes with coordination number six were analyzed in order to examine the efficacy of the ab initio calculations. Theoretical results suggest that the Double-Zeta Valence Potential (DZVP) and Sadlej basis sets are better than the 3-21G basis set. Our calculations also show that ab initio calculations identify the coordination number of cadmium complexes.

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Section: Introductionmentioning

confidence: 99%

Quantum Chemical Calculations of Cadmium Chemical Shifts in Inorganic Complexes

Kidambi

Ramamoorthy

2002

J. Phys. Chem. A

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“…Compound 5 was dissolved again in pyridine to crystallize out purple crystals for a single-crystal X-ray analysis. 1 [12] and that of 5 Hz for H b protons in Cd(tpp)(py) (py = pyridine) (1) [1]. The 1 H NMR spectrum (Fig.…”

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confidence: 98%

“…Previously, Ellis and coworkers reported the multinuclear ( 113 Cd, 15 N, 13 C, 1 H) NMR study of the pyridine adduct of cadmium meso-tetraphenylporphyrin Cd(tpp) (py) (py = pyridine) (1) and 15 N multiply labeled cadmium meso-tetraphenylporphyrin Cd([ 15 N 4 ]tpp)(py) (2) [1]. Amma et al [3] reported the crystal structures and 113 Cd NMR spectra of the piperidine adduct of (5, 10, 15, 20-tetraphenylporphyrinato)cadmium(II) Cd(tpp) (pip) AE o-xylene (pip = piperidine) (3) [2] and (5, 10, 15, 20-tetraphenylporphyrinato)cadmium(II)-bis(dioxane) solvate Cd(tpp) AE (dioxane) 2 (4).…”

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confidence: 99%

“…This bonding argument is further supported by the result that the upfield shift of $3.0 ppm [from 149.9 (obtained for free pyridine) to 146.9 ppm] was observed for the coordinated py-C 2,6 of 5 in toluene-d 8 . 1 The ring current effects seldom exceed 2 ppm for 13 C NMR [14,15]. Hence, the ring current contribution is relatively less important in determining the 13 C chemical shifts than proton shifts.…”

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confidence: 99%

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