Electronic and vibrational spectra of some rare earth trifluoromethanesulfonates crystals

Paul, Pralay; Ghosh, Manas; Neogy, D.; Mallick, Prabal Kumar

doi:10.1016/j.saa.2010.08.060

Cited by 4 publications

(4 citation statements)

References 16 publications

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“…The characteristics of the observed bands correspond, in general, to those of the La complex reported in our previous study [27]. The assignment of the CF 3 SO 3 − bands agrees with IR data on rare earth trifluoromethanesulfonate crystals in the literature [49]. The electronic nature of the metal-nitrogen bonding was investigated using the natural bond orbital (NBO) [26] and quantum theory of atoms in molecules (QTAIM) [29] models.…”

Section: R(iii) Bsupporting

confidence: 78%

Comparative Study of Complexes of Rare Earths and Actinides with 2,6-Bis(1,2,4-triazin-3-yl)pyridine

Kovács¹,

Apostolidis²,

Walter³

2019

Inorganics

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Complexes of group III metals (rare earth and actinides) with 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (BTP) have been investigated by computational (DFT) and, in limited cases, by experimental (FT-IR, X-ray) techniques with the goal of determining the characteristics of metal–ligand interactions. The DFT calculations using the M062X exchange-correlation functional revealed that metal–ligand distances correlate with the ionic radii of the metals, in agreement with available X-ray diffraction results on the Sc, Y, La, U, and Pu complexes. A related blue-shift trend could be observed in seven characteristic bands in the IR spectra associated with metal–ligand vibrations. The computations uncovered considerable charge transfer interactions, particularly in the actinide complexes, as important covalent contributions to the metal–ligand bonding. The covalent character of the metal–ligand bonds decreases in the actinides, from U to Cm.

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Section: R(iii) Bsupporting

confidence: 78%

Comparative Study of Complexes of Rare Earths and Actinides with 2,6-Bis(1,2,4-triazin-3-yl)pyridine

Kovács¹,

Apostolidis²,

Walter³

2019

Inorganics

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“…This has been performed by qualitative visual observation of the fundamentals by means of the GaussView program [47], facilitating the recognition of their main vibrational components. The bands of the CF 3 SO À 3 counter ions were supported by literature IR data on rare earth trifluoromethanesulfonate crystals [48]. The characterisation of selected important peaks of [La(BTP) 3 ](CF 3 SO 3 ) 3 is given in Table 4.…”

Section: Resultssupporting

confidence: 63%

‘Lanthanide contraction’ in [Ln(BTP)3](CF3SO3)3 complexes

et al. 2015

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The FTIR spectra of the complexes of lanthanides (Ln = La -Lu, except for the radioactive Pm) with 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine have been measured in both the mid-and far-IR ranges. The spectra revealed some characteristic bands shifting towards higher wavenumbers with increasing lanthanide atomic number. X-ray diffraction results on several (La, Pr, Nd, Sm, Eu, Tm and Yb) complexes revealed decreasing Lnligand distances in the same direction. DFT calculations using the M062X exchange-correlation functional have been performed on selected model complexes in order to uncover the 'lanthanide contraction' phenomenon and to assist the interpretation of the FTIR spectra. The stronger bonding due to 'lanthanide contraction' is supported by the computed charge transfer interactions. The vibrational study confirmed that the blueshifting bands can be attributed to significant Ln-ligand vibrations.

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“…Confocal Raman microscopy unambiguously confirmed the presence of the peroxide fragment. 1-Pr displayed a single isotopically sensitive vibration at 820 cm –1 , which falls within the range reported for other rare-earth peroxides. ,,, A peroxide stretch was not observed for 18 O 2 -derived 1-Pr , which we attribute to spectral overlap with a triflate C–F vibration ( v C–F = 770 cm –1 ; Theory: Δ 18 O– 18 O( 1-Pr ) = 47 cm –1 , v 18 O– 18 O ( 1-Pr ) = 773 cm –1 ). Attempts to crystallize the alcohol solvate, 1-Pr , only led to amorphous materials; however, introducing chelating O-donors, 18-crown-6 (18C6), and ethylene glycol (EG) furnished X-ray quality single crystals of the dimeric praseodymium peroxide, [Pr III 2 (O 2 2– ) (18c6) 2 (EG) 2 ][OTf] 4 ( 2-Pr ), in 72% yield from MeOH solutions layered with i PrOH (Figure ).…”

Section: Resultssupporting

confidence: 77%

Peroxide-Selective Reduction of O₂ at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide

et al. 2022

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Metal peroxides are key species involved in a range of critical biological and synthetic processes. Rare-earth (group III and the lanthanides; Sc, Y, La−Lu) peroxides have been implicated as reactive intermediates in catalysis; however, reactivity studies of isolated, structurally characterized rare-earth peroxides have been limited. Herein, we report the peroxide-selective (93−99% O 2 2-) reduction of dioxygen (O 2 ) at redox-inactive rare-earth triflates in methanol using a mild metallocene reductant, decamethylferrocene (Fc*). The first molecular praseodymium peroxide ([Pr III 2 (O 2 2−)-(18C6) 2 (EG) 2 ][OTf] 4 ; 18C6 = 18-crown-6, EG = ethylene glycol, − OTf = − O 3 SCF 3 ; 2-Pr) was isolated and characterized by singlecrystal X-ray diffraction, Raman spectroscopy, and NMR spectroscopy. 2-Pr displays high thermal stability (120 °C, 50 mTorr), is protonated by mild organic acids [pK a1 (MeOH) = 5.09 ± 0.23], and engages in electrophilic (e.g., oxygen atom transfer) and nucleophilic (e.g., phosphate-ester cleavage) reactivity. Our mechanistic studies reveal that the rate of oxygen reduction is dictated by metal-ion accessibility, rather than Lewis acidity, and suggest new opportunities for differentiated reactivity of redox-inactive metal ions by leveraging weak metal−ligand binding events preceding electron transfer.

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Electronic and vibrational spectra of some rare earth trifluoromethanesulfonates crystals

Cited by 4 publications

References 16 publications

Comparative Study of Complexes of Rare Earths and Actinides with 2,6-Bis(1,2,4-triazin-3-yl)pyridine

Comparative Study of Complexes of Rare Earths and Actinides with 2,6-Bis(1,2,4-triazin-3-yl)pyridine

‘Lanthanide contraction’ in [Ln(BTP)3](CF3SO3)3 complexes

Peroxide-Selective Reduction of O₂ at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide

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Electronic and vibrational spectra of some rare earth trifluoromethanesulfonates crystals

Cited by 4 publications

References 16 publications

Comparative Study of Complexes of Rare Earths and Actinides with 2,6-Bis(1,2,4-triazin-3-yl)pyridine

Comparative Study of Complexes of Rare Earths and Actinides with 2,6-Bis(1,2,4-triazin-3-yl)pyridine

‘Lanthanide contraction’ in [Ln(BTP)3](CF3SO3)3 complexes

Peroxide-Selective Reduction of O2 at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide

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Product

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Peroxide-Selective Reduction of O₂ at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide