Mössbauer-Active Transition Metals Other than Iron

Gütlich, Philipp; Bill, Eckhard; Trautwein, Alfred X.

doi:10.1007/978-3-540-88428-6_7

Cited by 3 publications

(4 citation statements)

References 413 publications

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“…This indicates that the relative change of the nuclear radius from the ground to the excited state (ΔR/R) in eq 1 is positive for the 99 Ru Mossbauer transition. 16 The δ calc values obtained by introducing the ρ 0 calc values into eq 4 are more comparable to those from the experiments for the singlet state than the others. However, almost no difference exists at an RMSD value of 0.07 mm s −1 .…”

Section: Calculation Of Mossbauer Spectroscopicsupporting

confidence: 61%

“…All Ru(II)–NO + and Ru(III)–NO 0 complexes show an increase in ρ 0 calc values in the order of L = Br – , Cl – , NH 3 , and CN – , correlating to an increase in δ exp . This indicates that the relative change of the nuclear radius from the ground to the excited state (Δ R / R ) in eq is positive for the 99 Ru Mössbauer transition . The δ calc values obtained by introducing the ρ 0 calc values into eq are more comparable to those from the experiments for the singlet state than the others.…”

Section: Resultsmentioning

confidence: 55%

“…The quadrupole splitting (Δ E Q ) values for a nuclear spin quantum number ( I ) of 3/2 can be formulated using the electric field gradients V ii ( i = x , y , z ) and the asymmetry parameter η = ( V xx – V yy )/ V zz : where V ii follows the order | V xx | ≤ | V yy | ≤ | V zz |, and Q 3/2 is the nuclear quadrupole moment of the Mössbauer nuclide when I = 3/2. The I values for the 99 Ru nuclide are 5/2 and 3/2 for the nuclear ground and excited states, respectively . We used the Q value for I = 3/2 and obtained Q 3/2 = 0.23 b, because the quadrupole splitting in 99 Ru Mössbauer studies often utilizes Δ E Q at I = 3/2.…”

Section: Computational Detailsmentioning

confidence: 99%

“…99 Ru Mossbauer spectroscopy is an experimental method that provides direct information on the coordination bonds between the Ru atom and ligands. 16 Greatrex et al studied the coordination bonds of several [Ru(NO)L 5 ] complexes, using 99 Ru Mossbauer spectroscopy, and indicated that the variation in bond strength is dependent on the ligands (L) by connecting with the ligand field strength estimated empirically. 17 Their study advanced the understanding of the coordination bonds of ruthenium−nitrosyl complexes.…”

Section: Introductionmentioning

confidence: 99%

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Density Functional Theory (DFT)-Based Bonding Analysis Correlates Ligand Field Strength with ⁹⁹Ru Mössbauer Parameters of Ruthenium–Nitrosyl Complexes

et al. 2019

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We applied density functional theory calculations to ruthenium–nitrosyl complexes, which are known to exist in high-level radioactive waste generating during reprocessing of spent nuclear fuel, to give a theoretical correlation between 99Ru Mössbauer spectroscopic parameters and ligand field strength for the first time. The structures of the series of complexes, [Ru(NO)L5] (L = Br–, Cl–, NH3, CN–), were modeled based on the corresponding single-crystal X-ray coordinates. The comparisons of the geometries and total energies between the different spin states suggested that the singlet spin state of [Ru(II)(NO+)L5] complexes were the most stable. This result was supported by the benchmark calculations of the 99Ru Mössbauer isomer shift (δ) and quadrupole splitting (ΔE Q) values. The calculated results of both the δ and ΔE Q values reproduced the experimental results by reported previously and increased in the order of L = Br–, Cl–, NH3, CN–. Finally, we estimated the ligand field strength (Δo) based on molecular orbitals, assuming C 4v symmetry and showed the increase of Δo values in that order, being consistent with well-known spectrochemical series of ligands. The increase attributes to the strengthening of the abilities of σ-donor and π-acceptor of the L-ligands to the Ru atom, resulting in the increase of the δ values. Furthermore, the increase of the σ-type donation into Ru d x 2–y 2 orbital and the π-type back-donation from Ru d xz , d yz orbitals in that order caused the decrease of the electron density along the Ru-NO axis, resulting in the increase of the ΔE Q values. This study is expected to contribute to the ligand design for the ruthenium–nitrosyl complexes, leading to the drug design for NO carrier and the decontamination of radioactive ruthenium from the ecological system, as well as the recovery of platinum-group metals from high-level radioactive waste.

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Section: Calculation Of Mossbauer Spectroscopicsupporting

confidence: 61%

Section: Resultsmentioning

confidence: 55%

Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Density Functional Theory (DFT)-Based Bonding Analysis Correlates Ligand Field Strength with ⁹⁹Ru Mössbauer Parameters of Ruthenium–Nitrosyl Complexes

et al. 2019

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On the Extreme Oxidation States of Iridium

Pyykkö

2015

Chemistry A European J

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It has recently been suggested that the oxidation states of Ir run from the putative -III in the synthesized solid Na3 [Ir(CO)3 ] to the well-documented +IX in the species IrO4 (+) . Furthermore, [Ir(CO)3 ](3-) was identified as an 18-electron species. A closer DFT study now finds support for this picture: The orbitals spanned by the 6s,6p,5d orbitals of the iridium are all occupied. Although some have considerable ligand character, the deviations from 18 e leave the orbital symmetries unchanged. The isoelectronic systems from Os(-IV) to Au(-I) behave similarly, suggesting further possible species. To paraphrase Richard P. Feynmann "there is plenty of room at the bottom".

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Synchrotron-based Nickel Mössbauer Spectroscopy

et al. 2016

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We used a novel experimental setup to conduct the first synchrotron-based (61)Ni Mössbauer spectroscopy measurements in the energy domain on Ni coordination complexes and metalloproteins. A representative set of samples was chosen to demonstrate the potential of this approach. (61)NiCr2O4 was examined as a case with strong Zeeman splittings. Simulations of the spectra yielded an internal magnetic field of 44.6 T, consistent with previous work by the traditional (61)Ni Mössbauer approach with a radioactive source. A linear Ni amido complex, (61)Ni{N(SiMe3)Dipp}2, where Dipp = C6H3-2,6-(i)Pr2, was chosen as a sample with an "extreme" geometry and large quadrupole splitting. Finally, to demonstrate the feasibility of metalloprotein studies using synchrotron-based (61)Ni Mössbauer spectroscopy, we examined the spectra of (61)Ni-substituted rubredoxin in reduced and oxidized forms, along with [Et4N]2[(61)Ni(SPh)4] as a model compound. For each of the above samples, a reasonable spectrum could be obtained in ∼1 d. Given that there is still room for considerable improvement in experimental sensitivity, synchrotron-based (61)Ni Mössbauer spectroscopy appears to be a promising alternative to measurements with radioactive sources.

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Mössbauer-Active Transition Metals Other than Iron

Cited by 3 publications

References 413 publications

Density Functional Theory (DFT)-Based Bonding Analysis Correlates Ligand Field Strength with ⁹⁹Ru Mössbauer Parameters of Ruthenium–Nitrosyl Complexes

Density Functional Theory (DFT)-Based Bonding Analysis Correlates Ligand Field Strength with ⁹⁹Ru Mössbauer Parameters of Ruthenium–Nitrosyl Complexes

On the Extreme Oxidation States of Iridium

Synchrotron-based Nickel Mössbauer Spectroscopy

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Mössbauer-Active Transition Metals Other than Iron

Cited by 3 publications

References 413 publications

Density Functional Theory (DFT)-Based Bonding Analysis Correlates Ligand Field Strength with 99Ru Mössbauer Parameters of Ruthenium–Nitrosyl Complexes

Density Functional Theory (DFT)-Based Bonding Analysis Correlates Ligand Field Strength with 99Ru Mössbauer Parameters of Ruthenium–Nitrosyl Complexes

On the Extreme Oxidation States of Iridium

Synchrotron-based Nickel Mössbauer Spectroscopy

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Product

Resources

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Density Functional Theory (DFT)-Based Bonding Analysis Correlates Ligand Field Strength with ⁹⁹Ru Mössbauer Parameters of Ruthenium–Nitrosyl Complexes

Density Functional Theory (DFT)-Based Bonding Analysis Correlates Ligand Field Strength with ⁹⁹Ru Mössbauer Parameters of Ruthenium–Nitrosyl Complexes