A convenient synthesis of 3-aryl-5-methylidene-2-thiohydantoins

3-Aryl-5-methylidene-2-thiohydantoins were constructed in one-pot reaction of aryl isothiocyanates and 3-morpholino- alanine in alkaline medium with the subsequent treatment with boiling hydrochloric acid.     

Reactivity of a N-Coordinated Germylene-Borane Complex: From Ge→B to Ge→Ga Coordination

Reactivity studies of the Ge^II→B complex L(Cl)Ge⋅BH₃ ( 1 ; L=2-Et₂NCH₂-4,6-tBu₂-C₆H₂) were performed to determine the effect on the Ge^II→B donation. N-coordinated compounds L(OtBu)Ge⋅BH₃ ( 2 ) and [LGe⋅BH₃]₂ ( 3 ) were prepared. The possible tuning of the Ge^II→B interaction was proved experimentally, yielding compounds 1-PPh₂-8-(LGe)-C₁₀H₆ ( 4 ) and L(Cl)Ge⋅GaCl₃ ( 5 ) without a Ge^II→B interaction. In 5 , an unprecedented Ge^II→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the Ge^II→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed.     

Periodicity of Two-Dimensional Bonding of Main Group Elements

In the periodic table the position of each atom follows the ‘aufbau’ principle of the individual electron shells. The resulting intrinsic periodicity of atomic properties determines the overall behavior of atoms in two-dimensional (2D) bonding and structure formation. Insight into the type and strength of bonding is the key in the discovery of innovative 2D materials. The primary features of 2D bonding and the ensuing monolayer structures of the main-group II–VI elements result from the number of valence electrons and the change of atom size, which determine the type of hybridization. The results reveal the tight connection between strength of bonding and bond length in 2D networks. The predictive power of the periodic table reveals general rules of bonding, the bonding-structure relationship, and allows an assessment of published data of 2D materials.     

Chemical bonding in representative astrophysically relevant neutral,cation, and anion HCnH chains

Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths. Building on our recent work, in this paper we add further evidence on the limitations of such an analysis and demonstrate the significant insight gained via natural bond analysis. Presently reported results include atomic charges, natural bond order and valence indices obtained from ab initio computations for representative members of the astrophysically relevant neutral and charged HC_2k/2k+1H chain family. They unravel a series of counter-intuitive aspects and/or help naive intuition in properly understanding microscopic processes, e.g., electron removal from or electron attachment to a neutral chain. Demonstrating that the Wiberg indices adequately quantify the chemical bonding structure of the HC_2k/2k+1H chains—while the often heavily advertised Mayer indices do not—represents an important message conveyed by the present study.     

Direct Transformation of Arenols Based on C—O Activation

In the view of substrate availability, atomic efficiency and cost, directly using arenols as coupling partners in cross‐coupling, would be one of the most attractive goals. Up to date, many efforts have been made to activate the C—O bond of phenols with different strategies, for example, through in‐situ formed intermediates, through a catalytic reductive dearomatization‐condensation‐rearomatization sequence or catalytic deoxygenation. In this review, we summarized recent advances in cross‐couplings of arenols as the electrophiles via C—O activation.     

Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

Theory of chemical bonds in metalloenzymes XXII: a concerted bond-switching mechanism for the oxygen–oxygen bond formation coupled with one electron transfer for water oxidation in the oxygen-evolving complex of photosystem II

ABSTRACT

QM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S₄ state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)₄–O₍₅₎ bond and the π*-LUMO of the Mn(V)₁=O₍₆₎ bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn₄O₆ cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)₁=O₍₆₎ bond to the σ*-LUMO of the Mn(IV)₄–O₍₅₎ bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)₄–O₍₅₎]^-? part is relaxed to the ?Mn(III)₄?…?O₍₅₎^- structure and the cation radical [O₍₆₎=Mn(V)₁]⁺ ? part is relaxed to the ⁺O₍₆₎–Mn(IV)₁? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)₄->Mn(III)₄ and Mn(V)₁->Mn(IV)₁. On the other hand, the O₍₅₎^- and O₍₆₎⁺ sites generated undergo the O–O bond formation in the CaMn₄O₆ cluster. The Ca(II) ion in the cubane- skeleton of the CaMn₄O₆ cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)₁=O₍₆₎ and σ*-LUMO of Mn(IV)₄–O₍₅₎, indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism.     

镧系金属一氢化物有效芯势研究

采用Cundari和Stevens等推导的有效芯势对镧系金属一氢化物进行了理论计算，以探讨镧系金属元素与氢的相互作用。结果表明所有镧系金属一氢化物基态时理论上是稳定的，最稳定的是SmH,最不稳定的是DyH;键长计算结果显示，基态时镧系金属一招兵买马花物有独立王国 收缩现象发生；红外振动频率理论计算值与实验结果一致；成键轨道中，金属原子轨道的贡献主要是s轨道和d轨道：从CeH至ErH(GdH)例外）随着外层电子的增加s轨道成分逐渐增大d轨道成分逐渐减小；从TmH和LuH（包括GdH)，成键轨道中金属原子轨道的贡献主要是d轨道，约为90％；约大多数镧系金属一氧化物的成键轨道中金属原子轨道f成分小于1％。     

用不确定度评价测量结果中的有效自由度的作用

论述了有效自由度的计算方法及有效自由度量值在分析测量结果中的应用。