Diversity of Chemical Bonding and Oxidation States in MS<sub>4</sub> Molecules of Group 8 Elements

Huang, Wei; Jiang, Ning; Schwarz, W. H. Eugen; Yang, Ping; Li, Jun

doi:10.1002/chem.201701117

Cited by 7 publications

(8 citation statements)

References 91 publications

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“…This order is even further reversed in superheavy element Rg. Such phenomenon has been noted in recent papers on the heavy d-elements, such as the particular stability of Hs 8+ O 4 and Hs 8+ S 4 . − Illustrated in Figure are the nonrelativistic (NR), scalar-relativistic (SR), and spin–orbit (SO) energy levels of Cu, Ag, Au, and Rg and the electron density radial distribution of the 7s and 6d orbitals of Rg. Clearly, the energy level of the Rg 7s valence-shell orbital is relativistically stabilized so strongly that it stays energetically lower than the destabilized Rg 6d orbitals and becomes significantly contracted radially.…”

Section: Resultsmentioning

confidence: 62%

Relativity–Induced Bonding Pattern Change in Coinage Metal Dimers M₂ (M = Cu, Ag, Au, Rg)

Wang

et al. 2018

Inorg. Chem.

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The periodic table provides a fundamental protocol for qualitatively classifying and predicting chemical properties based on periodicity. While the periodic law of chemical elements had already been rationalized within the framework of the nonrelativistic description of chemistry with quantum mechanics, this law was later known to be affected significantly by relativity. We here report a systematic theoretical study on the chemical bonding pattern change in the coinage metal dimers (Cu, Ag, Au, Rg) due to the relativistic effect on the superheavy elements. Unlike the lighter congeners basically demonstrating ns- ns bonding character and a 0 ground state, Rg shows unique 6d-6d bonding induced by strong relativity. Because of relativistic spin-orbit (SO) coupling effect in Rg, two nearly degenerate SO states, 0 and 2, exist as candidate of the ground state. This relativity-induced change of bonding mechanism gives rise to various unique alteration of chemical properties compared with the lighter dimers, including higher intrinsic bond energy, force constant, and nuclear shielding. Our work thus provides a rather simple but clear-cut example, where the chemical bonding picture is significantly changed by relativistic effect, demonstrating the modified periodic law in heavy-element chemistry.

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Section: Resultsmentioning

confidence: 62%

Relativity–Induced Bonding Pattern Change in Coinage Metal Dimers M₂ (M = Cu, Ag, Au, Rg)

Wang

et al. 2018

Inorg. Chem.

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“…Bk is somewhat of an exception to this trend, as the Bk center is being oxidized, with a ΔG of oxidation of only 0.01 eV, essentially the same as that of Fc 0 /Fc + couple and contrasting with its neighbors Cm and Cf which both have values over 1 eV. Metal oxidation states are known to have some dependence on complexing ligands, 73,74 and this redox data gives further evidence of the stabilization of An(IV) ions by HOPO, recently observed by Deblonde et al in their investigation of Bk 4+ complexation by HOPO. 33 These differences in redox potential correspond to the changes in the An spin density observed in Figure 6.…”

Section: Inorganic Chemistrymentioning

confidence: 99%

Bond Covalency and Oxidation State of Actinide Ions Complexed with Therapeutic Chelating Agent 3,4,3-LI(1,2-HOPO)

et al. 2018

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for heavier actinides, reflecting increased energy degeneracy driven covalency and concomitant orbital mixing between the 5f 24 orbitals of the An ions and the π orbitals of the ligand. Notably, the ability of this ligand to either accept or donate electron 25 density as needed from its pyridine rings is found to be key to its extraordinary stability across the actinide series. ■ INTRODUCTION27 Radiological contamination incidents can result in widespread 28 radiation exposure to both local and remote regions. 29 Representing an extreme recent example, the 2011 Fukushima 30 Daiichi Nuclear Power Plant accident resulted in the dispersal 31 of several radionuclides across a wide area, including portions of 32 the continental U.S.1 Actinide (An) and lanthanide (Ln) fission 33 product species are likely to be major components of such 34 contamination events, and it is therefore necessary to 35 thoroughly understand and study the behavior of these ions 36 in environmental and biological systems. Internal contamination of human populations in the event of 38 a radiological incident, whether accidental or intentional, is of 39 critical concern. Once internalized, An ions transit rapidly 40 throughout the bloodstream and are primarily deposited in the 41 liver and bones (uranium is an exception and preferentially 42 deposits in the kidneys rather than in the liver), from which 43 elimination occurs very slowly. 3,4 Uptake and deposition of 44 these ions present severe health risks due to both their 45 The present work uses density functional theory (DFT) 120 combined with extended X-ray absorption fine structure 121 (EXAFS) measurements to advance our current understanding 122 of An-3,4,3-LI(1,2-HOPO) complexes. Their structure, ther-123 modynamics, electronic structures, and redox properties are 124 investigated across the An series up to Es, with both formally 125 An(III) and An(IV) ions. The similarity of 3,4,3-LI(1,2-126 HOPO) to other biological complexants and the wealth of 127 excellent experimental information on this system ensures that 128 a fundamental understanding of An-3,4,3-LI(1,2-HOPO) 129 complexation will have applications beyond this single ligand, 130 and presents an opportunity to study trends in An-ligand 131 Other than the exceptions described above, the fit model 243 obtained from calculated structures describes the data well 244 (Figure 2). Generally speaking, the EXAFS data are consistent 245 with the HOPO complex structure calculations for the nearest 246 neighbor M(III)−O pair distances with the largest deviation 247 occurring with [Am(HOPO)] − . In addition, the Cf−C/N 248 average bond length differs from calculation, but the calculation 249 also shows a broad distribution width for the 8 bonds in this t1 250 shell. Table 1 compares the EXAFS bond length results to 251 those derived from the DFT calculations for the first two shells. 252 Further details of the methods and results are available in 253 Supporting Information (pp S11−S15). Figure S6 for thermodynamic calculations...

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“…Oxidation state (OS) is one of the most basic and useful, though fuzzy, concepts in the chemistry of elements and a fundamental criterion for their classification into similarity groups. − The highest OS values were the primary parameters for the arrangement of the elements in the early periodic tables, designed by Meyer and by Mendeleev in the 1860s. − The OS of an atom (or a group of atoms) in a compound is defined through the combination of experimental observations and theoretical model descriptions; namely, first, one draws a Lewis formula that should realistically describe the most important electronic aspects of chemical bonding in this compound, and then, the bonding pairs between two different atoms are assigned to the more electronegative one. , Obviously, the definition of OS must not be mixed up with the definition of effective charges …”

Section: Introductionmentioning

confidence: 99%

“…18−20 Regarding the highest OS, the question is: How many electrons of an atomic electron-rich valence shell can be chemically activated? Apparently, not all six valence electrons of the O-(2s2p) 6 shell but all of iso-valence-electronic S-(3s3p) 6 or Se-(4s4p) 6 shells from the same group 16; not all eight electrons of Fe-(3d4s) 8 but all of Ru-(4d5s) 8 or Os-(5d6s) 8 , all three elements being in group 8; not all six electrons of Nd-(4f5d6s) 6 but all of U-(5f6d7s) 6 . Under which chemical conditions can the whole valence shell of p-or d-or f-block elements become activated?…”

Section: Introductionmentioning

confidence: 99%

Electronic Structure and Spectroscopic Properties of Group-7 Tri-Oxo-Halides MO₃X (M = Mn–Bh, X = F–Ts)

Jiang

et al. 2021

Inorg. Chem.

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The 24 trioxide halide molecules MO 3 X of the manganese group (M = Mn−Bh; X = F−Ts), which are iso-valence-electronic with the famous MnO 4 − ion, have been quantum-chemically investigated by quasi-relativistic density-functional and ab initio correlated approaches. Geometric and electronic structures, valence and oxidation numbers, vibrational and electronic spectral properties, energetic stabilities of the monomers in the gas phase, and the decay mode of MnO 3 F have been investigated. The light Mn-3d species are most strongly electron-correlated, indicating that the concept of a closed-shell Lewis-type singleconfigurational structure [Mn +7 (d 0 ) O −2 (p 6 ) 3 F − (p 6 )] reaches its limits. The concept of real-valued spin orbitals φ(r)•α and φ(r)•β breaks down for the heavy Bh-6d, At-6p and Ts-7p elements because of the dominating spin−orbit coupling. The vigorous decomposition of MnO 3 F at ambient conditions starts by the autocatalyzed release of n O 2 and the formation of Mn m O 3m−2n F m clusters, triggered by the electron-depleted "oxylic" character of the oxide ligands in MnO 3 X.

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Diversity of Chemical Bonding and Oxidation States in MS₄ Molecules of Group 8 Elements

Cited by 7 publications

References 91 publications

Relativity–Induced Bonding Pattern Change in Coinage Metal Dimers M₂ (M = Cu, Ag, Au, Rg)

Relativity–Induced Bonding Pattern Change in Coinage Metal Dimers M₂ (M = Cu, Ag, Au, Rg)

Bond Covalency and Oxidation State of Actinide Ions Complexed with Therapeutic Chelating Agent 3,4,3-LI(1,2-HOPO)

Electronic Structure and Spectroscopic Properties of Group-7 Tri-Oxo-Halides MO₃X (M = Mn–Bh, X = F–Ts)

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Diversity of Chemical Bonding and Oxidation States in MS4 Molecules of Group 8 Elements

Cited by 7 publications

References 91 publications

Relativity–Induced Bonding Pattern Change in Coinage Metal Dimers M2 (M = Cu, Ag, Au, Rg)

Relativity–Induced Bonding Pattern Change in Coinage Metal Dimers M2 (M = Cu, Ag, Au, Rg)

Bond Covalency and Oxidation State of Actinide Ions Complexed with Therapeutic Chelating Agent 3,4,3-LI(1,2-HOPO)

Electronic Structure and Spectroscopic Properties of Group-7 Tri-Oxo-Halides MO3X (M = Mn–Bh, X = F–Ts)

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Product

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Diversity of Chemical Bonding and Oxidation States in MS₄ Molecules of Group 8 Elements

Relativity–Induced Bonding Pattern Change in Coinage Metal Dimers M₂ (M = Cu, Ag, Au, Rg)

Relativity–Induced Bonding Pattern Change in Coinage Metal Dimers M₂ (M = Cu, Ag, Au, Rg)

Electronic Structure and Spectroscopic Properties of Group-7 Tri-Oxo-Halides MO₃X (M = Mn–Bh, X = F–Ts)