Satoru Nakashima - Academia.edu (original) (raw)
Papers by Satoru Nakashima
Applied Physics A, Jun 7, 2022
Radiochimica Acta, Nov 17, 2018
Coal-fly-ash is one of the major byproducts of coal-based power plant in which naturally occurrin... more Coal-fly-ash is one of the major byproducts of coal-based power plant in which naturally occurring radioactive materials (NORMs) are drastically enriched compared to those of feed coals. Thus, improper management of fly-ash may introduce additional radioactivity to the surrounding environment and cause radiological risk. So, in order to study the distribution of radionuclides in soil around a coal-based power plant and to evaluate their radiological risk, soil, coal and fly-ash samples were analyzed by using a HPGe detector for U-238, Ra-226, Th-232 and K-40 radioactivity concentrations. Furthermore, soil minerals were also studied by X-ray diffractometer to assess the mineralogical provenance of the radionuclides. Mean radioactivity concentrations (in Bq·kg−1) of U-238, Ra-226, Th-232 and K-40 in soil samples are 102.9±41.4, 63.6±7.4, 103.4±13.9 and 494.2±107.5, respectively which are comparatively higher than the typical world mean value. Elevated levels of radioactivity are likely due to the presence of illite, kaolinite, monazite, rutile and zircon minerals in the soil samples rather than technogenic contributions from the power plant. Furthermore, mean soil contamination factor (CF) are close to unity and mean pollution load index (PLI) is below unity while the average radium equivalent activity (Raeq in Bq·kg−1), external hazard index (Hex), absorbed γ dose rate (D in nGyh−1), annual effective dose rate (E in mSv·y−1) and excess lifetime cancer risk (ELCR in Sv−1) are 249.5±21.7, 0.67±0.06, 114.2±9.4, 0.20±0.02, 4.9×10−4±0.4×10−4, respectively, which are within the permissible limit. Thus, in terms of radioactivity concentrations and associated environmental and radiological indices, the effect of the power plant is insignificant.
Environmental Monitoring and Assessment, 2019
The original version of this article unfortunately contained an error in equaton 1. The denominat... more The original version of this article unfortunately contained an error in equaton 1. The denominator ε of equation 1 was missing. The corrected equation 1 is shown below. A ¼ cps sample −cps BG ε Â I γ The original article has been corrected.
RADIOISOTOPES, 2017
Iron(II) assembled complexes [Fe(NCX) 2 (L) 2 ] (X=S, Se and BH 3 ; L=2,5-dimethyl-1,4-bis(4-pyri... more Iron(II) assembled complexes [Fe(NCX) 2 (L) 2 ] (X=S, Se and BH 3 ; L=2,5-dimethyl-1,4-bis(4-pyridyl)benzene (dmbpb) and 2,3,5,6-tetramethyl-1,4-bis(4-pyridyl)benzene (tmbpb)) were synthesized to investigate the effect of substituent on the spin crossover (SCO) behavior. PXRD revealed that the structure is different between dmbpb and tmbpb complexes, while the structures are independent of anionic ligands. 57 Fe Mӧssbauer spectroscopy and magnetic susceptibility measurement revealed that the SCO occurs in the case of [Fe(NCSe) 2 (dmbpb) 2 ] and [Fe(NCBH 3) 2 (dmbpb) 2 ] but the SCO is not observed in other complexes. The quadrupole splitting (Q.S.) value in high-spin state decreased in the order of S>Se>BH 3 for dmbpb complexes but S>BH 3 >Se for tmbpb complexes. It was suggested that electron distribution is different between dmbpb and tmbpb complexes. Transition temperature for [Fe(NCBH 3) 2 (dmbpb) 2 ] was 128 K, which is lower than that of the corresponding complex bridged with 1,4-bis(4-pyridyl)benzene.
RADIOISOTOPES, 2019
An investigation concerning the transfer of radioactive caesium from soil to ears of rice in the ... more An investigation concerning the transfer of radioactive caesium from soil to ears of rice in the paddy fields of Fukushima after the Fukushima Dai-ichi Nuclear Power Plant accident has been carried out. Because the investigation in 2013 revealed relatively higher concentrations of radioactive 137 Cs and 134 Cs in the rice ears from one of the neighboring four contiguous fields, the aim of the present research carried out in 2014 and 2015 was to investigate the features of the paddy field where the contaminated rice ears were produced. It was revealed that the concentrations of radioactive 137 Cs and 134 Cs in the soil decreased with increasing depth, despite the fact that the cultivation was carried out in the preceding year. The Cs depth dependency was different among the fields. The 137 Cs and 134 Cs penetrated more deeply in the field where a relatively higher radioactive caesium concentration in ears of rice was observed. The difference depended on the variation of grain size distribution of soil, which affected the uptake of caesium in the rice ears. Four fields were cultivated in 2013 and 2014, although the upper two fields were not cultivated in 2015. Some locations showed relatively higher concentrations of radioactive 137 Cs and 134 Cs for rice ears in the two bottom fields in 2015, compared to the concentrations in 2013 and 2014, suggesting the possibility of a change of grain size distribution of soil.
Environmental Monitoring and Assessment, 2018
To study the level of radioactivity concentrations from a coal-based power plant (Barapukuria, Ba... more To study the level of radioactivity concentrations from a coal-based power plant (Barapukuria, Bangladesh) and to estimate the associated radiological hazards, coal and associated combustion residuals from the power plant were analyzed by gamma-ray spectrometry with high-purity germanium (HPGe) detector. The results reveal that the mean radioactivity (Bq kg −1) concentrations in feed coal samples are 66.
Inorganics, 2017
Assembled complexes, [Fe(NCX) 2 (bpanth) 2 ] n (X = S, Se, BH 3 ; bpanth = 9,10-bis (4-pyridyl)an... more Assembled complexes, [Fe(NCX) 2 (bpanth) 2 ] n (X = S, Se, BH 3 ; bpanth = 9,10-bis (4-pyridyl)anthracene), were synthesized. The iron for the three complexes was in temperature-independent high spin state by 57 Fe Mössbauer spectroscopy and magnetic susceptibility measurement. X-ray structural analysis revealed the interpenetrated structure of [Fe(NCS) 2 (bpanth) 2 ] n. In the local structure around the iron atom, the coordinated pyridine planes were shown to be a parallel type, which is in accordance with the results investigated by density functional theory (DFT) calculation. This complex (X = S) has CH-π interactions between the H atom of coordinated pyridine and the neighboring anthracene of the other 2D grid. It was suggested that the interpenetrated structure was supported by the stabilization of CH-π interaction, and this intermolecular interaction forced the relatively unstable parallel structure. That is, the unstable local structure is compensated by the stabilization due to intermolecular interaction, which controlled the spin state as high spin state.
PROCEEDINGS OF INTERNATIONAL CONFERENCE ON NUCLEAR SCIENCE, TECHNOLOGY, AND APPLICATION 2020 (ICONSTA 2020), 2021
J. Chem. Soc., Dalton Trans., 1995
The mixed-valence states of biferrocene derivatives with long alkyl substituents, which have a la... more The mixed-valence states of biferrocene derivatives with long alkyl substituents, which have a layered structure, have been investigated by means of 57Fe Mossbauer spectroscopy and X-ray powder diffraction. An interesting even–odd character in the number of carbon atoms of the alkyl chain is found in the relationship between the crystal structure and the mixed-valence state. The mixed-valence states of 1′,1‴-bis(dodecyl)-1,1″-biferrocenium triiodide change in accordance with a transformation of the crystal structure in the solid state. An X-ray diffraction analysis for this salt obtained from dichloromethane at 0 °C showed that both the cation and the anion are situated at a centre of symmetry and the dodecyl substituent has the all-trans conformation. The layers are located in the ab plane.
Journal of the Chemical Society, Dalton Transactions, 1996
The relation between the mixed-valence state and crystal structure of 1′,1‴-didecyl- and 1′,1‴-bi... more The relation between the mixed-valence state and crystal structure of 1′,1‴-didecyl- and 1′,1‴-bis(undecyl)-1,1″-biferrocenium triiodide has been studied by means of 57Fe Mossbauer spectroscopy and X-ray powder diffraction. The salts with even numbers of carbon atoms in the alkyl chain show a phase transition between two types of layered structures, accompanied by a change in mixed-valence state. Iodine-129 Mossbauer spectroscopy was applied to determine the electronic state of the triiodide anion in the biferrocenium salts. A change in the electronic state accompanied by a phase transition was observed in the case of the 1′,1‴-didecyl derivative.
Journal of Radioanalytical and Nuclear Chemistry, 2014
Mixed crystals of cobalt and zinc were synthesized using 1,3-bis(4pyridyl)propane (bpp) as bridgi... more Mixed crystals of cobalt and zinc were synthesized using 1,3-bis(4pyridyl)propane (bpp) as bridging ligand and NCS − as anion. Red crystals and blue crystals were obtained. Powder X-ray diffraction patterns showed that the former is in 2D interpenetrated structure, while the latter has the same structure with Zn(NCS) 2 (bpp). Iron ion was introduced both into the red crystals and blue crystals of the mixed crystals of cobalt with zinc. 57 Fe Mössbauer spectrum of the red crystals showed a main doublet of Fe II high-spin state at 78 K, while the spectrum of blue crystals did not show Fe II high-spin state at 78 K.
![Research paper thumbnail of Computational Study on Thermal Spin-Crossover Behavior for Coordination Polymers Possessingtrans-[Fe(NCS)2(pyridine)4] Unit](https://attachments.academia-assets.com/85677461/thumbnails/1.jpg)
](Bulletin of the Chemical Society of Japan, 2015
Fe(II) spin-crossover (SCO) phenomenon for fifteen sets of coordination polymers possessing a tra... more Fe(II) spin-crossover (SCO) phenomenon for fifteen sets of coordination polymers possessing a trans-[Fe(NCS) 2-(pyridine) 4 ] unit is investigated by means of density functional calculations. Constrained geometry optimization is applied to Fe(NCS) 2 (pyridine) 4 models by fixing the dihedral angle between Fe-NCS axis and pyridine plane. Zero-point corrected energy difference between HS and LS, ¦E 0 HL , by TPSSh single point calculation reproduces successfully the experimental SCO-on and SCO-off behaviors for most compounds. In order to investigate the origin of whether SCO behavior occurs or not, we perform Mulliken's overlap population analysis to wavefunction in valence region. Overlap population between d-orbital of Fe atom and all atomic orbitals of six N atoms enables us to assign the kind of d-orbital type molecular orbitals. Calculating ligand field splitting (¦ o) obtained by population analysis, we find good correlation between ¦ o of LS and ¦E 0 HL indicating that the bonding of LS state depends on the switching behavior of SCO-on/off. Furthermore, combining the ligand field theory with quantum chemical calculation, we obtain the ¦ o value of the crossing point where ¦E 0 HL is zero as ca. 4.61 eV.
Nucl Instrum Meth Phys Res B, 1993
AIP Conference Proceedings, 2005
X‐ray structural analyses revealed the inclusion of biphenyl into the assembled complexes and the... more X‐ray structural analyses revealed the inclusion of biphenyl into the assembled complexes and the composition was confirmed as Fe2(NCS)4(bpy)4(biphenyl)5, Fe(NCS)2(bpa)2(biphenyl)2, and Fe(NCSe)2(bpa)2biphenyl. 57Fe Mossbauer spectroscopy revealed that the spin state remained high spin but the QS value changed by introducing biphenyl molecule in the assembled complex.
Journal of Organometallic Chemistry, 2015
Selective mono-lithiation method of bis(cyclopentadienyl)osmium(II) (osmocene) was established. I... more Selective mono-lithiation method of bis(cyclopentadienyl)osmium(II) (osmocene) was established. Iodoosmocene(C 5 H 4 I)Os(C 5 H 5) (OcI), which is the first monohalogenated product of osmocene, was prepared by the reaction of lithioosmocene with I 2. Ullmann coupling reaction of iodoosmoene allowed to prepare biosmocene(C 5 H 5)Os(m 2-h 5 :h 5-C 10 H 8)Os(C 5 H 5) (OcOc). OcOc reacted with I 2 , giving mixedvalence biosmocenium salt [(C 5 H 5)Os II (m 2-h 5 :h 5-C 10 H 8) (C 5 H 5)Os IV I]I 3 (A). The structure of A was determined by single crystal X-ray structural analysis. The intramolecular electron transfer reaction between Os II and Os IV was observed by using 1 H NMR spectroscopy, accompanied by the exchange of I À anion between the two units. The activation energy of the electron transfer reaction was estimated and the value was larger than that of binuclear ruthenocenium salt [(C 5 H 5)Ru II (m 2-h 5 :h 5-C 10 H 8) (C 5 H 5)Ru IV I]I 3 (B).
Inorganic chemistry, Jan 20, 2015
We performed a theoretical investigation for the selectivity of Eu(III)/Am(III) ions depending on... more We performed a theoretical investigation for the selectivity of Eu(III)/Am(III) ions depending on the donor atoms by means of all-electron ZORA-DFT calculation. We estimated their selectivity as the relative stability in the complex formation reaction. The B2PLYP functional reproduced the experimental selectivity in which S- and N-donor ligands favor Am(III) ion, but O-donor ligand favors Eu(III) ion. Mulliken's bond overlap population analysis revealed that the contribution of the f orbital to the bonding was small or zero for Eu complex, whereas it was large for Am complex. The bonding nature of the f orbital for Am ion was the bonding type to S- and N-donor ligands, while it was the antibonding type to O-donor ligand. It was suggested that the difference in the bonding nature between the f orbital in the metal and the donor atoms determines the selectivity of Eu(III)/Am(III) by donor ligands.
Applied Physics A, Jun 7, 2022
Radiochimica Acta, Nov 17, 2018
Coal-fly-ash is one of the major byproducts of coal-based power plant in which naturally occurrin... more Coal-fly-ash is one of the major byproducts of coal-based power plant in which naturally occurring radioactive materials (NORMs) are drastically enriched compared to those of feed coals. Thus, improper management of fly-ash may introduce additional radioactivity to the surrounding environment and cause radiological risk. So, in order to study the distribution of radionuclides in soil around a coal-based power plant and to evaluate their radiological risk, soil, coal and fly-ash samples were analyzed by using a HPGe detector for U-238, Ra-226, Th-232 and K-40 radioactivity concentrations. Furthermore, soil minerals were also studied by X-ray diffractometer to assess the mineralogical provenance of the radionuclides. Mean radioactivity concentrations (in Bq·kg−1) of U-238, Ra-226, Th-232 and K-40 in soil samples are 102.9±41.4, 63.6±7.4, 103.4±13.9 and 494.2±107.5, respectively which are comparatively higher than the typical world mean value. Elevated levels of radioactivity are likely due to the presence of illite, kaolinite, monazite, rutile and zircon minerals in the soil samples rather than technogenic contributions from the power plant. Furthermore, mean soil contamination factor (CF) are close to unity and mean pollution load index (PLI) is below unity while the average radium equivalent activity (Raeq in Bq·kg−1), external hazard index (Hex), absorbed γ dose rate (D in nGyh−1), annual effective dose rate (E in mSv·y−1) and excess lifetime cancer risk (ELCR in Sv−1) are 249.5±21.7, 0.67±0.06, 114.2±9.4, 0.20±0.02, 4.9×10−4±0.4×10−4, respectively, which are within the permissible limit. Thus, in terms of radioactivity concentrations and associated environmental and radiological indices, the effect of the power plant is insignificant.
Environmental Monitoring and Assessment, 2019
The original version of this article unfortunately contained an error in equaton 1. The denominat... more The original version of this article unfortunately contained an error in equaton 1. The denominator ε of equation 1 was missing. The corrected equation 1 is shown below. A ¼ cps sample −cps BG ε Â I γ The original article has been corrected.
RADIOISOTOPES, 2017
Iron(II) assembled complexes [Fe(NCX) 2 (L) 2 ] (X=S, Se and BH 3 ; L=2,5-dimethyl-1,4-bis(4-pyri... more Iron(II) assembled complexes [Fe(NCX) 2 (L) 2 ] (X=S, Se and BH 3 ; L=2,5-dimethyl-1,4-bis(4-pyridyl)benzene (dmbpb) and 2,3,5,6-tetramethyl-1,4-bis(4-pyridyl)benzene (tmbpb)) were synthesized to investigate the effect of substituent on the spin crossover (SCO) behavior. PXRD revealed that the structure is different between dmbpb and tmbpb complexes, while the structures are independent of anionic ligands. 57 Fe Mӧssbauer spectroscopy and magnetic susceptibility measurement revealed that the SCO occurs in the case of [Fe(NCSe) 2 (dmbpb) 2 ] and [Fe(NCBH 3) 2 (dmbpb) 2 ] but the SCO is not observed in other complexes. The quadrupole splitting (Q.S.) value in high-spin state decreased in the order of S>Se>BH 3 for dmbpb complexes but S>BH 3 >Se for tmbpb complexes. It was suggested that electron distribution is different between dmbpb and tmbpb complexes. Transition temperature for [Fe(NCBH 3) 2 (dmbpb) 2 ] was 128 K, which is lower than that of the corresponding complex bridged with 1,4-bis(4-pyridyl)benzene.
RADIOISOTOPES, 2019
An investigation concerning the transfer of radioactive caesium from soil to ears of rice in the ... more An investigation concerning the transfer of radioactive caesium from soil to ears of rice in the paddy fields of Fukushima after the Fukushima Dai-ichi Nuclear Power Plant accident has been carried out. Because the investigation in 2013 revealed relatively higher concentrations of radioactive 137 Cs and 134 Cs in the rice ears from one of the neighboring four contiguous fields, the aim of the present research carried out in 2014 and 2015 was to investigate the features of the paddy field where the contaminated rice ears were produced. It was revealed that the concentrations of radioactive 137 Cs and 134 Cs in the soil decreased with increasing depth, despite the fact that the cultivation was carried out in the preceding year. The Cs depth dependency was different among the fields. The 137 Cs and 134 Cs penetrated more deeply in the field where a relatively higher radioactive caesium concentration in ears of rice was observed. The difference depended on the variation of grain size distribution of soil, which affected the uptake of caesium in the rice ears. Four fields were cultivated in 2013 and 2014, although the upper two fields were not cultivated in 2015. Some locations showed relatively higher concentrations of radioactive 137 Cs and 134 Cs for rice ears in the two bottom fields in 2015, compared to the concentrations in 2013 and 2014, suggesting the possibility of a change of grain size distribution of soil.
Environmental Monitoring and Assessment, 2018
To study the level of radioactivity concentrations from a coal-based power plant (Barapukuria, Ba... more To study the level of radioactivity concentrations from a coal-based power plant (Barapukuria, Bangladesh) and to estimate the associated radiological hazards, coal and associated combustion residuals from the power plant were analyzed by gamma-ray spectrometry with high-purity germanium (HPGe) detector. The results reveal that the mean radioactivity (Bq kg −1) concentrations in feed coal samples are 66.
Inorganics, 2017
Assembled complexes, [Fe(NCX) 2 (bpanth) 2 ] n (X = S, Se, BH 3 ; bpanth = 9,10-bis (4-pyridyl)an... more Assembled complexes, [Fe(NCX) 2 (bpanth) 2 ] n (X = S, Se, BH 3 ; bpanth = 9,10-bis (4-pyridyl)anthracene), were synthesized. The iron for the three complexes was in temperature-independent high spin state by 57 Fe Mössbauer spectroscopy and magnetic susceptibility measurement. X-ray structural analysis revealed the interpenetrated structure of [Fe(NCS) 2 (bpanth) 2 ] n. In the local structure around the iron atom, the coordinated pyridine planes were shown to be a parallel type, which is in accordance with the results investigated by density functional theory (DFT) calculation. This complex (X = S) has CH-π interactions between the H atom of coordinated pyridine and the neighboring anthracene of the other 2D grid. It was suggested that the interpenetrated structure was supported by the stabilization of CH-π interaction, and this intermolecular interaction forced the relatively unstable parallel structure. That is, the unstable local structure is compensated by the stabilization due to intermolecular interaction, which controlled the spin state as high spin state.
PROCEEDINGS OF INTERNATIONAL CONFERENCE ON NUCLEAR SCIENCE, TECHNOLOGY, AND APPLICATION 2020 (ICONSTA 2020), 2021
J. Chem. Soc., Dalton Trans., 1995
The mixed-valence states of biferrocene derivatives with long alkyl substituents, which have a la... more The mixed-valence states of biferrocene derivatives with long alkyl substituents, which have a layered structure, have been investigated by means of 57Fe Mossbauer spectroscopy and X-ray powder diffraction. An interesting even–odd character in the number of carbon atoms of the alkyl chain is found in the relationship between the crystal structure and the mixed-valence state. The mixed-valence states of 1′,1‴-bis(dodecyl)-1,1″-biferrocenium triiodide change in accordance with a transformation of the crystal structure in the solid state. An X-ray diffraction analysis for this salt obtained from dichloromethane at 0 °C showed that both the cation and the anion are situated at a centre of symmetry and the dodecyl substituent has the all-trans conformation. The layers are located in the ab plane.
Journal of the Chemical Society, Dalton Transactions, 1996
The relation between the mixed-valence state and crystal structure of 1′,1‴-didecyl- and 1′,1‴-bi... more The relation between the mixed-valence state and crystal structure of 1′,1‴-didecyl- and 1′,1‴-bis(undecyl)-1,1″-biferrocenium triiodide has been studied by means of 57Fe Mossbauer spectroscopy and X-ray powder diffraction. The salts with even numbers of carbon atoms in the alkyl chain show a phase transition between two types of layered structures, accompanied by a change in mixed-valence state. Iodine-129 Mossbauer spectroscopy was applied to determine the electronic state of the triiodide anion in the biferrocenium salts. A change in the electronic state accompanied by a phase transition was observed in the case of the 1′,1‴-didecyl derivative.
Journal of Radioanalytical and Nuclear Chemistry, 2014
Mixed crystals of cobalt and zinc were synthesized using 1,3-bis(4pyridyl)propane (bpp) as bridgi... more Mixed crystals of cobalt and zinc were synthesized using 1,3-bis(4pyridyl)propane (bpp) as bridging ligand and NCS − as anion. Red crystals and blue crystals were obtained. Powder X-ray diffraction patterns showed that the former is in 2D interpenetrated structure, while the latter has the same structure with Zn(NCS) 2 (bpp). Iron ion was introduced both into the red crystals and blue crystals of the mixed crystals of cobalt with zinc. 57 Fe Mössbauer spectrum of the red crystals showed a main doublet of Fe II high-spin state at 78 K, while the spectrum of blue crystals did not show Fe II high-spin state at 78 K.
Bulletin of the Chemical Society of Japan, 2015
Fe(II) spin-crossover (SCO) phenomenon for fifteen sets of coordination polymers possessing a tra... more Fe(II) spin-crossover (SCO) phenomenon for fifteen sets of coordination polymers possessing a trans-[Fe(NCS) 2-(pyridine) 4 ] unit is investigated by means of density functional calculations. Constrained geometry optimization is applied to Fe(NCS) 2 (pyridine) 4 models by fixing the dihedral angle between Fe-NCS axis and pyridine plane. Zero-point corrected energy difference between HS and LS, ¦E 0 HL , by TPSSh single point calculation reproduces successfully the experimental SCO-on and SCO-off behaviors for most compounds. In order to investigate the origin of whether SCO behavior occurs or not, we perform Mulliken's overlap population analysis to wavefunction in valence region. Overlap population between d-orbital of Fe atom and all atomic orbitals of six N atoms enables us to assign the kind of d-orbital type molecular orbitals. Calculating ligand field splitting (¦ o) obtained by population analysis, we find good correlation between ¦ o of LS and ¦E 0 HL indicating that the bonding of LS state depends on the switching behavior of SCO-on/off. Furthermore, combining the ligand field theory with quantum chemical calculation, we obtain the ¦ o value of the crossing point where ¦E 0 HL is zero as ca. 4.61 eV.
Nucl Instrum Meth Phys Res B, 1993
AIP Conference Proceedings, 2005
X‐ray structural analyses revealed the inclusion of biphenyl into the assembled complexes and the... more X‐ray structural analyses revealed the inclusion of biphenyl into the assembled complexes and the composition was confirmed as Fe2(NCS)4(bpy)4(biphenyl)5, Fe(NCS)2(bpa)2(biphenyl)2, and Fe(NCSe)2(bpa)2biphenyl. 57Fe Mossbauer spectroscopy revealed that the spin state remained high spin but the QS value changed by introducing biphenyl molecule in the assembled complex.
Journal of Organometallic Chemistry, 2015
Selective mono-lithiation method of bis(cyclopentadienyl)osmium(II) (osmocene) was established. I... more Selective mono-lithiation method of bis(cyclopentadienyl)osmium(II) (osmocene) was established. Iodoosmocene(C 5 H 4 I)Os(C 5 H 5) (OcI), which is the first monohalogenated product of osmocene, was prepared by the reaction of lithioosmocene with I 2. Ullmann coupling reaction of iodoosmoene allowed to prepare biosmocene(C 5 H 5)Os(m 2-h 5 :h 5-C 10 H 8)Os(C 5 H 5) (OcOc). OcOc reacted with I 2 , giving mixedvalence biosmocenium salt [(C 5 H 5)Os II (m 2-h 5 :h 5-C 10 H 8) (C 5 H 5)Os IV I]I 3 (A). The structure of A was determined by single crystal X-ray structural analysis. The intramolecular electron transfer reaction between Os II and Os IV was observed by using 1 H NMR spectroscopy, accompanied by the exchange of I À anion between the two units. The activation energy of the electron transfer reaction was estimated and the value was larger than that of binuclear ruthenocenium salt [(C 5 H 5)Ru II (m 2-h 5 :h 5-C 10 H 8) (C 5 H 5)Ru IV I]I 3 (B).
Inorganic chemistry, Jan 20, 2015
We performed a theoretical investigation for the selectivity of Eu(III)/Am(III) ions depending on... more We performed a theoretical investigation for the selectivity of Eu(III)/Am(III) ions depending on the donor atoms by means of all-electron ZORA-DFT calculation. We estimated their selectivity as the relative stability in the complex formation reaction. The B2PLYP functional reproduced the experimental selectivity in which S- and N-donor ligands favor Am(III) ion, but O-donor ligand favors Eu(III) ion. Mulliken's bond overlap population analysis revealed that the contribution of the f orbital to the bonding was small or zero for Eu complex, whereas it was large for Am complex. The bonding nature of the f orbital for Am ion was the bonding type to S- and N-donor ligands, while it was the antibonding type to O-donor ligand. It was suggested that the difference in the bonding nature between the f orbital in the metal and the donor atoms determines the selectivity of Eu(III)/Am(III) by donor ligands.