ChemInform Abstract: Oxidation State 10 Exists.

DFT electronic structure calculations indicate the existence of oxidation state 10 in the T_d structure of PtO₄²⁺.     

Oxidation State 10 Exists

In a recent paper, Wang et al. found an iridium‐containing compound with a formal oxidation state of 9. ⁵ This is the highest oxidation state ever found in a stable compound. To learn if this is the highest chemical oxidation state possible, Kohn–Sham density functional theory was used to study various compounds, including PdO₄²⁺, PtO₄²⁺, PtO₃F₂²⁺, PtO₄OH⁺, PtO₅, and PtO₄SH⁺, in which the metal has an oxidation state of 10. It was found that PtO₄²⁺ has a metastable state that is kinetically stable with a barrier height for decomposition of 31 kcal mol⁻¹ and a calculated lifetime of 0.9 years. All other compounds studied would readily decompose to lower oxidation states.     

Beyond Oxides: Nitride as a Ligand in a Neutral IrIXNO3 Molecule Bearing a Transition Metal at High Oxidation State

Theoretical calculations utilizing relativistic ZORA Hamiltonian point to the conceivable existence of an IrNO₃ molecule in C_3v geometry. This minimum is shown to correspond to genuine nonavalent iridium nitride trioxide, which is a neutral analogue of cationic [IrO₄]⁺ species detected recently. Despite the presence of nitride anion, the molecule is protected by substantial barriers exceeding 200 kJ mol⁻¹ against transformations leading, for example, to global minimum (O=)₂Ir−NO, which contains metal at a lower formal oxidation state.     

Pt的氧化状态对甲醇氧化活性的影响

采用NaBH4还原法制备了XC-72碳黑负载的Pt电催化剂,并在化学还原后用H2O2处理部分催化剂以改变Pt的氧化状态,以期改善Pt活性中心上水的离解而提高催化活性.X射线光电子能谱结果表明,经H2O2处理的催化剂含有较多的氧化态Pt.通过循环伏安法和记时电流法考察了经处理和未经处理的催化剂在酸性条件下的甲醇氧化的催化...     

Controlling the Oxidation State of Pt Single Atoms for Maximizing Catalytic Activity

Single-atom catalysts (SACs) have emerged as promising materials in heterogeneous catalysis. Previous studies reported controversial results about the relative level in activity for SACs and nanoparticles (NPs). These works have focused on the effect of metal atom arrangement, without considering the oxidation state of the SACs. Here, we immobilized Pt single atoms on defective ceria and controlled the oxidation state of Pt SACs, from highly oxidized (Pt⁰: 16.6 at %) to highly metallic states (Pt⁰: 83.8 at %). The Pt SACs with controlled oxidation states were then employed for oxidation of CO, CH₄, or NO, and their activities compared with those of Pt NPs. The highly oxidized Pt SACs presented poorer activities than Pt NPs, whereas metallic Pt SACs showed higher activities. The Pt SAC reduced at 300 °C showed the highest activity for all the oxidations. The Pt SACs with controlled oxidation states revealed a crucial missing link between activity and SACs.     

Pt（111）和Pt3Ni（111）表面上CO催化氧化反应的密度泛函理论研究

采用密度泛函理论,对Pt(111)和Pt3Ni(111)表面上CO和O的单独吸附、共吸附以及CO的氧化反应进行了系统的研究. 结果表明, Pt3Ni(111)表面上CO的吸附弱于Pt(111)表面, O的吸附明显强于Pt(111)表面. 两个表面表现出相似的CO催化氧化活性. 表面Ni的存在不但稳定了O的吸附,同时也降低了过渡态O的能量.     

铂基催化剂用于柴油烃氧化

The catalytic performance of Pt-based catalysts for the total oxidation of hydrocarbons was investigated.The activity of supported Pt catalysts(Pt/Al2O3,Pt/ZrO2,Pt/TiO2,and Pt/H-ZSM-5)depends on the metal oxide support.Pt/Al2O3 showed the highest catalytic activity when the catalysts were aged at 750°C for 50 h in air.The activity of Pt/Al2O3 was dependent on the valence state of the Pt surface.Pt/Al2O3 with the Pt surface in the metallic state was more active than with the surface in the cationic state.The surface density of acid and basic sites on the Al2O3 support controlled the valence state of the Pt surface and stability of the Pt particles in the highly dispersed state,respectively.     

Density functional calculations on CO attached to PtnRu(10−n) (n = 6–10) clusters

B3LYP and SCF‐Xα calculations have been performed on Pt_nRu_(10−n)CO (n = 6–10) clusters. The work aims to simulate the adsorption of CO on the (111) surface of platinum metal and to examine the electronic effects that arise when some Pt atoms are replaced with Ru. Adsorption energies and Pt C and C O stretching frequencies have been calculated for each cluster. Ru does affect the electronic structure of the clusters, the calculated adsorption energies, and frequencies, the Pt C frequency more than the C O. The donation‐backbonding mechanism that accompanies the shift in CO stretching frequency that occurs when CO adsorbs on platinum does not explain the differences in frequency shift observed in CO on various Pt/Ru surfaces. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 77: 589–598, 2000     

Diiron(III)–μ‐Fluoro Bisporphyrins: Effect of Bridging Ligand on the Metal Spin State

A hitherto unknown family of diiron(III)–μ‐fluoro bisporphyrins has been synthesized and structurally characterized. Fluoride abstraction from SbF₆^? and BF₄^? resulted in the synthesis of the μ‐fluoro complexes of ethane‐ and ethene‐bridged diiron(III) bisporphyrins. Two such complexes were structurally characterized, which revealed a single fluoro bridge between two iron centers with a remarkably bent Fe‐F‐Fe unit. Although isoelectronic with the μ‐hydroxo complexes, the μ‐fluoro species are quite divergent in terms of the electronic structure and properties. UV/Vis spectroscopy of the μ‐fluoro complex exhibits a large redshift (ca. 18 nm) of the Soret band in comparison to their μ‐hydroxo analog. Combined analysis by single crystal X‐ray structure determination and Mössbauer and ¹H NMR spectroscopy revealed the presence of two equivalent iron(III) centers in the μ‐fluoro complexes in both solid and solution phases. In contrast, the iron(III) centers of the μ‐hydroxo complexes are known to be inequivalent. Variable‐temperature magnetic studies show a weak antiferromagnetic interaction between the iron(III) centers of the μ‐fluoro complexes with coupling constants (J) ranging from ?33 to ?40 cm^?1. The experimental results were further supported by DFT calculations.     

Alkyliodines in High Oxidation State: Enhanced Synthetic Possibilities and Accelerated Catalyst Turn-Over

In contrast to aryliodine(III) compounds, which have matured into a particularly attractive class of oxidants in modern synthesis, the synthetic potential of related alkyliodine(III) derivatives has remained widely underestimated. This is surprising since several unique synthetic possibilities arise directly from the low stability of their central carbon–iodine bond. In this respect, these high-oxidation-state iodine compounds resemble environmentally benign variants of the prominent metal counterparts such as those derived from palladium, nickel and copper. This Concept article summarizes the general reactivity trends in alkyliodine(III) chemistry and discusses selected examples of their strategic use as highly reactive, transient species in organic synthesis and homogeneous catalysis.     

High Correlation between Oxidation Loci on Graphene Oxide

Recent experiments have shown the coexistence of both large unoxidized and oxidized regions on graphene oxide (GO), but the underlying mechanism for the formation of the GO atomic structure remains unknown. Now, using density functional calculations, 52 oxidation pathways for local pyrene structures on GO were identified, and a kinetic profile for graphene oxidation with a high correlation between oxidation loci was proposed, which is different from the conventional view, which entails a random distribution of oxidation loci. The high correlation is an essential nature of graphene oxidation processes and can be attributed to three crucial effects: 1) breaking of delocalized π bonds, 2) steric hindrance, and 3) hydrogen‐bond formation. This high correlation leads to the coexistence of both large unoxidized and oxidized regions on GO. Interestingly, even in oxidized regions on GO, some small areas of sp²‐hybridized domains, similar to “islands”, can persist because of steric effects.     

Nature of the Transition State in Peroxyl Radical Recombination

We have carried out an ab initio calculation of the potential surface for the reaction CH₃O₄H CH₂=O + O₂ + H₂O. We have established the structure of the transition state and studied the dependence of the energy barrier on the size of the basis and whether electron correlation is taken into account. We have studied the electronically excited terms for the participants in this reaction and we have established the mechanism for the formation of chemiluminescence emitters in this reaction.     

Oxidation Effects on the Electronic Properties of Hydrogenated Silicon Clusters

The geometric and electronic properties of some hydrogenated silicon clusters in the presence of oxygen on the surface have been investigated.The density functional theory with generalized gradient approximation functional was applied in our calculations.By calculating the total energy,the double bond Si=O is shown to be more stable than the bridge bond Si-O-Si for large size oxidized clusters.The results of Mulliken population analysis indicate that a so-called passivation effect is enhanced by oxidization effects.From the energy band structures and density of states,we find that some localized states are induced by the p-orbital of O atom mainly and reduce the energy gaps substantially.     

Aromaticity Relocation in Perylene Derivatives upon Two‐Electron Oxidation To Form Anthracene and Phenanthrene

We prepared perylene dications 1 ²⁺ and 2 ²⁺ by using “capped” perylene derivatives, and for the first time, successfully obtained single crystals of a perylene dication 1 ²⁺ that enabled us to perform its structural analysis. We realized that the substituted aryl groups on perylene control the positions of positive charges, thus the remaining electronic system satisfies Clar's sextet rule toward the highest number of localized sextets. Experimental and theoretical evidence proved that Clar's aromatic π‐sextet rule could be applied even for the dicationic perylenes in a very simple way.     

Oxidative Addition of Halogens to Homoleptic Perfluoromethyl or Perfluorophenyl Derivatives of Platinum(II): A Comparative Study

Chlorocarbon solvents (solv=CH₂Cl₂, CHCl₃) are suggested to play an active role in the oxidative addition of halogens, X₂ (X=Cl, Br, I), to homoleptic d⁸ perfluoromethyl and ‐phenyl platinum(II ) species [Pt(R^F)₄]^2? (R^F=CF₃, C₆F₅). The perfluoromethyl group, CF₃, has been found to be considerably less prone to undergo reductive elimination processes, and is, therefore, more suitable for stabilizing organoplatinum(IV ) derivatives (see scheme).