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Emel’yanov, V. A.; Байдина, И. А.; Khranenko, S. P.; Gromilov, S. A.; Ильин, М. А.; Belyaev, A. V.

doi:10.1023/a:1024928913498

Cited by 12 publications

(5 citation statements)

References 2 publications

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“… a Values shown in parentheses represent the standard deviation to the averaged bond lengths. b Data taken from ref . c Data taken from ref . d Data taken from ref . e Data taken from ref . …”

Section: Resultsmentioning

confidence: 99%

“…Single-crystal X-ray coordinates for the four [Ru(NO)L 5 ] complexes were obtained from the Cambridge Structural Database (CSD) and used as the starting structures for geometry optimization calculations. The CSD codes included ACIGOI, IRUHEI, JERYAH, and ZOZSIS for complexes with L = Br – , Cl – , NH 3 , and CN – , respectively. Figure shows the 3D illustrations of [Ru(NO)L 5 ] complexes possessing octahedral coordination spheres.…”

Section: Computational Detailsmentioning

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: Resultsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

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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“…Ru(NO)Cl 5 ] 2À + H 2 O # trans-[Ru(NO)Cl 4 (H 2 O)] À + Cl À (K B 0.31), trans-[Ru(NO)Cl 4 (H 2 O)] À + H 2 O # mer-[Ru(NO)Cl 3 (H 2 O) 2 ] + Cl À K B 0.79.The resulting aquachlorocomplexes are weakly acidic:6,7 trans-[Ru(NO)Cl 4 (H 2 O)] À # trans-[Ru(NO)Cl 4 (OH)] 2À + H + (pK a B 6), mer-[Ru(NO)(H 2 O) 2 Cl 3 ] # mer-[Ru(NO)(H 2 O)Cl 3 (OH)] À + H + (pK a1 B 5),a Nikolaev Institute of Inorganic Chemistry, 3 Acad. Lavrentiev Ave., Novosibirsk, 630090, Russia.…”

mentioning

confidence: 99%

Synthesis and crystal structure of nitrosoruthenium complexes cis-[Ru(NO)Py₂Cl₂(OH)] and cis-[Ru(NO)Py₂Cl₂(H₂O)]Cl. Photoinduced transformations of cis-[Ru(NO)Py₂Cl₂(OH)]

et al. 2016

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“…For the related cationic trans ‐[RuNO(NH 3 ) 4 X] 2+ complexes, the shift is larger (0.12 Å) for X equal to nitrate or hydroxyl,, and is similar to the chloride complex . The RuNO fragment is close to linear with 176.26(8)° angle and the Ru–N and N–O bonds having usual distances of 1.7420(8) and 1.1338(11) Å respectively , , …”

Section: Resultsmentioning

confidence: 85%

Synthesis of the Ruthenium Nitrosyl Complex with Coordinated Ammonia and Pyridine at Room Temperature

Vorobyev

Костин

Байдина

et al. 2020

Zeitschrift anorg allge chemie

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The reaction of nitrate ruthenium complex, fac-[RuNO(NH 3 ) 2 (NO 3 ) 3 ], with pyridine resulted in cis-[RuNO(NH 3 ) 2 Py 2 (NO 3 )](NO 3 ) 2 ·H 2 O with 84 % yield of the product at room temperature. Addition of any solvent leads to the reaction failure; the excess of pyridine fulfilled the role of a solvent. The DFT simulation of the dissociative mechanism reveals that the nitrate loss from cis-position to NO occurs more easily than for trans-coordinated nitrate. This conclusion is in agreement with the X-ray determined struc-* V. Vorobyev

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Cited by 12 publications

References 2 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

Synthesis and crystal structure of nitrosoruthenium complexes cis-[Ru(NO)Py₂Cl₂(OH)] and cis-[Ru(NO)Py₂Cl₂(H₂O)]Cl. Photoinduced transformations of cis-[Ru(NO)Py₂Cl₂(OH)]

Synthesis of the Ruthenium Nitrosyl Complex with Coordinated Ammonia and Pyridine at Room Temperature

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Untitled

Cited by 12 publications

References 2 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

Synthesis and crystal structure of nitrosoruthenium complexes cis-[Ru(NO)Py2Cl2(OH)] and cis-[Ru(NO)Py2Cl2(H2O)]Cl. Photoinduced transformations of cis-[Ru(NO)Py2Cl2(OH)]

Synthesis of the Ruthenium Nitrosyl Complex with Coordinated Ammonia and Pyridine at Room Temperature

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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

Synthesis and crystal structure of nitrosoruthenium complexes cis-[Ru(NO)Py₂Cl₂(OH)] and cis-[Ru(NO)Py₂Cl₂(H₂O)]Cl. Photoinduced transformations of cis-[Ru(NO)Py₂Cl₂(OH)]