Epoxidation of Alkenes by Peracids: From Textbook Mechanisms to a Quantum Mechanically Derived Curly-Arrow Depiction

Using the intrinsic bond orbital (IBO) analysis based on accurate quantum mechanical calculations of the reaction path for the epoxidation of propene using peroxyacetic acid, we find that the four commonly used curly arrows for representing this reaction mechanism are insufficient and that seven curly arrows are required as a result of changes to σ and π bonding interactions, which are usually neglected in all textbook curly arrow representations. The IBO method provides a convenient quantitative method for deriving curly arrows in a rational manner rather than the normal ad hoc representations used ubiquitously in teaching organic chemistry.     

Research on Chemical Reactivity of Nitrotriazolam in Its Process of Preparation

Chemical reaction possibility was described quantitatively for the case of nitrotriazolam preparation with 2-clonazepam by using the data of two quantum chemical reactivity indices: net electrophilicity index and Wiberg bond order. Furthennore, relevant reaction mechanism was derived from tlie aspect of quantum chemistry. The results show that the indices used can quantitatively explain the chemical reactivity and reaction mechanism of the nitrotriazolam preparation. To validate the universal applicability of the proposed approach, the authors continued to use the quantum chemical reactivity indices to describe some classic chemical reactions, expecting to predict major issues related to physical organic chemistry, such as new chemical reactions and their mechanisms.     

Real‐time quantum chemistry

Significant progress in the development of efficient and fast algorithms for quantum chemical calculations has been made in the past two decades. The main focus has always been the desire to be able to treat ever larger molecules or molecular assemblies—especially linear and sublinear scaling techniques are devoted to the accomplishment of this goal. However, as many chemical reactions are rather local, they usually involve only a limited number of atoms so that models of about 200 (or even less) atoms embedded in a suitable environment are sufficient to study their mechanisms. Thus, the system size does not need to be enlarged, but remains constant for reactions of this type that can be described by less than 200 atoms. The question then arises how fast one can obtain the quantum chemical results. This question is not directly answered by linear‐scaling techniques. In fact, ideas such as haptic quantum chemistry (HQC) or interactive quantum chemistry require an immediate provision of quantum chemical information which demands the calculation of data in “real time.” In this perspective, we aim at a definition of real‐time quantum chemistry, explore its realm and eventually discuss applications in the field of HQC. For the latter, we elaborate whether a direct approach is possible by virtue of real‐time quantum chemistry. © 2012 Wiley Periodicals, Inc.     

Ethers on Si(001): A Prime Example for the Common Ground between Surface Science and Molecular Organic Chemistry

By using computational chemistry it has been shown that the adsorption of ether molecules on Si(001) under ultrahigh vacuum conditions can be understood with classical concepts of organic chemistry. Detailed analysis of the two‐step reaction mechanism—1) formation of a dative bond between the ether oxygen atom and a Lewis acidic surface atom and 2) nucleophilic attack of a nearby Lewis basic surface atom—shows that it mirrors acid‐catalyzed ether cleavage in solution. The O−Si dative bond is the strongest of its kind, and the reactivity in step 2 defies the Bell–Evans–Polanyi principle. Electron rearrangement during C−O bond cleavage has been visualized with a newly developed method for analyzing bonding, which shows that the mechanism of nucleophilic substitutions on semiconductor surfaces is identical to molecular S_N2 reactions. Our findings illustrate how surface science and molecular chemistry can mutually benefit from each other and unexpected insight can be gained.     

A Consistent System of Curved Electron Arrows

Many students of organic chemistry find it difficult to properly use electron arrows. Traditional arrows do not end at one type of location. Whereas the vast majority end at an atom, an arrow that indicates formation of a bond points to a bond instead. Rethinking electron arrows leads to the following four rules, which form a consistent system:1. An electron arrow always begins at an electron pair, either bonding or nonbonding. One arrow begins at the nucleophilic electron pair, if any.2. An electron pair always remains attached to an atom, normally indicated by its arrow.3. An electron arrow always ends at an atom, not at a bond. One arrow ends at the electrophilic atom, if an.4. In a series of arrows for one mechanistic step, a succeeding arrow begins by the atom where the preceding arrow ends.This system of electron arrows is superior because the rules can be more generally applied, the arrows reflect the nucleophilicity of electron pairs, the arrows carry more meaning, the arrows in a series flow more directly from one to the next, and the arrows clearly prescribe products.     

煤显微组分分子结构模型的量子化学研究

采用分子力学和半经验量子化学方法，研究了神木煤显微组分的分子结构模型，比较了镜质组和惰质组分子模型的能量构成、不同类型键的键长和键裂解能。研究结果表明，扭转能和范德华能是分子中的主要作用力，取代基对体系能量有明显影响，烷基取代基使体系能量增加，而苯基取代基使体系能量降低；脂肪C—C键长比芳香C—C键长长，说明脂肪C—C在受热过程中比芳香C—C更容易断裂分解。对各键裂解能的计算结果表明，Car—Cal键的裂解能高于Cal—Cal，Car—O醚键的裂解能高于Cal—O醚键。而惰质组结构模型中除C—O醚键外，各键的裂解能均高于镜质组，说明惰质组结构模型比镜质组有较高的热稳定性。     

Application of physical organic methods to the investigation of organometallic reaction mechanisms

For the past 75 years, physical organic chemistry has been the foundation for the elucidation of mechanisms, and the understanding of structure/activity relationships, in organic chemistry. The rational design of experiments and the critical analysis of data have been the hallmarks of this field. In this Perspective, we revisit some of the studies carried out during the past 30 years in which our group has used the tools of physical organic chemistry to investigate the mechanisms of a variety of organometallic reactions. The Perspective covers a broad spectrum of metal-mediated reactions including organic reductions, alkene, carbon monoxide and nitric oxide migratory insertion reactions, C-H bond activation, and the reactions of metal-heteroatom bonds with organic molecules. These studies, along with similar ones carried out in other groups, have demonstrated that the principles and methods of physical organic chemistry have adapted well to the study of organometallic reaction mechanisms. The understanding obtained in this way has aided the development of useful metal-mediated reactions in a wide range of areas, especially in industrial catalysis and in applications to problems in organic synthesis.     

Stoichiometric and catalytic reactivity of organometallic fragments supported on inorganic oxides

The reaction of some organometallic complexes with the surfaces of inorganic oxides leads to the formation of surface organometallic complexes, chemically bound to the surface yet retaining many features of their molecular structure. These surface organometallic complexes can therefore be considered to belong to both the molecular and solid states. In cases where such complexes have been structurally characterised, their reactivity can be interpreted with molecular concepts. In this review article, the stoichiometric and catalytic reactivity of some relatively well-defined surface organometallic fragments is surveyed. Many elementary steps which have precedent in molecular organometallic chemistry and homogeneous catalysis have now been demonstrated with surface organometallic fragments, including reversible ligand binding, oxidative addition, reductive elimination, protonation, heterolytic metal—carbon bond cleavage, electrophilic CH bond activation and insertion into metal—carbon bonds. In some cases, the supported organometallic complexes are highly effective low temperature catalysts, a phenomenon which is not always observed with molecular analogues nor with conventionally prepared heterogeneous catalysts. Applications of surface organometallic chemistry to catalytic alkane hydrogenolysis, olefin isomerisation and hydrogenation, the Fischer—Tropsch synthesis and the water—gas shift reaction are discussed. Proposed mechanisms for several representative catalytic cycles are presented.     

Recent advances in the use of phosphorus-centered radicals in organic chemistry

This tutorial review aims at presenting recent contributions dealing with organic chemistry of organophosphorus radicals. The first part briefly lays out the physical organic background of such intermediates. In a second part the use of organophosphorus radicals possessing a P-H bond that can undergo homolytic cleavage as alternative mediators is detailed. The third part is focused on radical additions of phosphorus-centered radicals to unsaturated compounds, an old reaction that is being rejuvenated. Lastly, radical eliminations of phosphorus-centered radical are introduced in the fourth part. Most of the latter are relatively novel reactions, and have never been reviewed previously.     

Comments on the status of the chemical bond in methods of quantum chemistry

Chemists do not take the view that chemistry can be derived from quantum mechanics by computations too literally; the difficulties are illustrated by the double bond concept. Quantum mechanics is very useful, but recent calculations have been mainly concerned with physical properties rather than chemical processes. In general, the chemical formula plays a central role in all interpretation of quantum-chemical results, thus suggesting that the chemical bond is a preexistent notion. Moreover, the Born–Oppenheimer approximation seems to be necessary for deriving the existence of bonds between atoms previously assigned to suitable positions. Recent analyses by Claverie and Diner, Woolley, Primas, and others are briefly recalled, concluding with an expression of hope that use of more general Hamiltonians can lead to progress in obtaining a fully independent quantum theory of chemistry.     

Electron transfer mechanism and photochemistry of ferrioxalate induced by excitation in the charge transfer band

The photoredox reaction of ferrioxalate after 266/267 nm excitation in the charge transfer band has been studied by means of ultrafast extended X-ray absorption fine structure (EXAFS) analysis, optical transient spectroscopy, and quantum chemistry calculations. The Fe-O bond length changes combined with the transient spectra and kinetics have been measured and in combination with ultrahigh frequency density functional theory (UHF/DFT) calculations are used to determine the photochemical mechanism for the Fe(III) to Fe(II) redox reaction. The present data and the results obtained with 266/267 nm excitations strongly suggest that the primary reaction is the dissociation of the Fe-O bond before intramolecular electron transfer occurs. Low quantum yield electron photodetachment from ferrioxalate has also been observed.     

基于钯催化C-H键活化的多米诺反应

近年来,多米诺反应作为一种合成复杂分子的高效手段已得到有机合成化学家的广泛关注。该反应过程中,不需改变反应条件和添加试剂,中间体也无需分离和提纯,实现了原子经济和环境友好。通过C-H键活化直接构建碳-碳键和碳-杂原子键,大大拓展了传统偶联反应的底物范围,同样具有高原子经济性,已经广泛地作为多米诺反应中的一个高效步骤。此外,钯催化剂运用广泛,能够与多种官能团兼容,是多米诺反应的理想金属催化剂。本文综述了基于钯催化C-H键活化的多米诺反应的最新研究进展,以反应中钯的价态变化进行分类,介绍有关反应的特点、优势及其在天然产物合成中的应用。     

The detailed mechanism of the Dushman reaction explored by computer

Since 1926 investigations of the Dushman reaction have relied mainly upon “constant-rate” measurements, usually by instrumental methods. Since about that time, the confusion surrounding this venerable reaction has been growing. In part, the confusion arises because the reaction involves reactive intermediate species that have not been studied directly—and may never be. Alternative detailed mechanisms have been assumed with little restraint. One of these, which is built around H₂I₂O₃, has been explored by computer with promising results. The mechanism seems capable of reducing the confusion now attending the Dushman reaction and others related to it.     

基于平均影响值的反向传播神经网络方法用于提高密度泛函理论计算Y—NO键均裂能精度

将基于平均影响值(Mean impact value,MIV)的反向传播神经网络(Back propagation neural netowrk,BPNN)(MIV-BPNN)方法用于提高密度泛函理论(Density functional theory,DFT)计算Y—NO(Y=N,S,O及C)键均裂能的精度.利用量子化学计算和MIV-BPNN联合方法计算92个含Y—NO键的有机分子体系的均裂能.结果表明,相对于单一的密度泛函理论B3LYP/6-31G(d)方法,利用全参数下的BPNN方法计算92个有机分子均裂能的均方根误差从22.25 kJ/mol减少到1.84 kJ/mol,而MIV-BPNN方法使均方根误差减少到1.36 kJ/mol,可见B3LYP/6-31G(d)和MIV-BPNN联合方法可以提高均裂能的量子化学计算精度,并可预测实验上无法获取的均裂能值.     

Polarization charge densities provide a predictive quantification of hydrogen bond energies

A systematic density functional theory based study of hydrogen bond energies of 2465 single hydrogen bonds has been performed. In order to be closer to liquid phase conditions, different from the usual reference state of individual donor and acceptor molecules in vacuum, the reference state of donors and acceptors embedded in a perfect conductor as simulated by the COSMO solvation model has been used for the calculation of the hydrogen bond energies. The relationship between vacuum and conductor reference hydrogen bond energies is investigated and interpreted in the light of different physical contributions, such as electrostatic energy and dispersion. A very good correlation of the DFT/COSMO hydrogen bond energies with conductor polarization charge densities of separated donor and acceptor atoms was found. This provides a method to predict hydrogen bond strength in solution with a root mean square error of 0.36 kcal mol(-1) relative to the quantum chemical dimer calculations. The observed correlation is broadly applicable and allows for a predictive quantification of hydrogen bonding, which can be of great value in many areas of computational, medicinal and physical chemistry.     

Toward a physical understanding of electron-sharing two-center bonds. I. General aspects

In 1916, Lewis and Kossel laid the empirical ground for the electronic theory of valence, whose quantum theoretical foundation was uncovered only slowly. We can now base the classification of the various traditional chemical bond types in a threefold manner on the one- and two-electron terms of the quantum-physical Hamiltonian (kinetic, atomic core attraction, electron repulsion). Bond formation is explained by splitting up the real process into two physical steps: (i) interaction of undeformed atoms and (ii) relaxation of this nonstationary system. We aim at a flexible bond energy partitioning scheme that can avoid cancellation of large terms of opposite sign. The driving force of covalent bonding is a lowering of the quantum kinetic energy density by sharing. The driving force of heteropolar bonding is a lowering of potential energy density by charge rearrangement in the valence shell. Although both mechanisms are quantum mechanical in nature, we can easily visualize them, since they are of one-electron type. They are however tempered by two-electron correlations. The richness of chemistry, owing to the diversity of atomic cores and valence shells, becomes intuitively understandable with the help of effective core pseudopotentials for the valence shells. Common conceptual difficulties in understanding chemical bonds arise from quantum kinematic aspects as well as from paradoxical though classical relaxation phenomena. On this conceptual basis, a dozen different bond types in diatomic molecules will be analyzed in the following article. We can therefore examine common features as well as specific differences of various bonding mechanisms.     

Features of Mechanistic Organic Chemistry already Present in 1910

Abstract

The sub-discipline of physical organic chemistry, a hybrid of organic and physical chemistry, made the study of the mechanisms of chemical reactions its task, using kinetics as the main tool. Perusal of the monograph by N. V. Sidgwick, Organic Chemistry of Nitrogen, which fulfils an explicit research programme in physical organic chemistry, serves here as an index to the status of this sub-discipline at the turn of the twentieth century. Many among the major concepts not only were fully formed, they were operative too. Sidgwick's book is at the root of the organized study of organic reaction mechanisms. This paternity begs to be more generally recognized. That this is not yet the case is due to Sidgwick's name having been associated almost exclusively to his later work, when he helped to usher in quantum chemical ideas. It is thus concluded that the mechanistic paradigm was already in place by 1910.     

硅杂四元环化合物的合成和反应

硅杂四元环化合物在有机硅化学中是一类非常重要的小分子环系化合物, 广泛应用于有机化学、金属有机化学以及材料化学. 环上只含有一个硅原子的硅杂环丁烷可以通过γ-卤代丙基硅烷的Grignard反应、Si＝C键与烯烃的 [2＋2]环加成反应以及硅杂环丙烷的扩环反应合成, 环上只含有一个硅原子的硅杂环丁烯可以通过格氏试剂或锂试剂参与的Si—C键的关环反应、硅杂环丁烷的转化反应、硅卡宾对C—H键的插入反应、Si＝C键与炔烃的[2＋2]环加成反应以及二炔基硅烷的分子内成环反应等途径合成. 硅杂环丁烷和硅杂环丁烯由于存在环张力和具有一定的Lewis酸性, 能够通过扩环反应生成五元和六元含硅杂环化合物, 也能够通过开环反应生成不同结构的有机硅分子和聚合物, 抑或实现有机反应在温和条件下的转化.     

Early impact of quantum physics on chemistry: George Hevesy’s work on rare earth elements and Michael Polanyi’s absorption theory

After Heitler and London published their pioneering work on the application of quantum mechanics to chemistry in 1927, it became an almost unquestioned dogma that chemistry would soon disappear as a discipline of its own rights. Reductionism felt victorious in the hope of analytically describing the chemical bond and the structure of molecules. The old quantum theory has already produced a widely applied model for the structure of atoms and the explanation of the periodic system. This paper will show two examples of the entry of quantum physics into more classical fields of chemistry: inorganic chemistry and physical chemistry. Due to their professional networking, George Hevesy and Michael Polanyi found their ways to Niels Bohr and Fritz London, respectively, to cooperate in solving together some problems of classical chemistry. Their works on rare earth elements and adsorption theory throws light to the application of quantum physics outside the reductionist areas. They support the heuristic and persuasive value of quantum thinking in the 1920–1930s. Looking at Polanyi’s later oeuvre, his experience with adsorption theory could be a starting point of his non-justificationist philosophy.     

Quantum chemical study of the primary step of ozone addition at the double bond of ethylene

The mechanism of the primary step of the interaction between ozone and the double bond of ethylene has been investigated by various methods of quantum chemistry (MP2, QCISD, CCSD, MRMP2) and density functional theory (PBE0, OPTX, CPW91, B3PW91, OLYO, B3LYP, BLYP). The kinetics of two reaction pathways, namely, concerted ozone addition via a symmetric transition state (Criegee mechanism) and nonconcerted ozone addition via a biradical transition state (DeMore mechanism) has been calculated. Both mechanisms are describable well in the single-determinant approximation by the QCISD, CCSD, B3LYP, and PBE0 methods and in the multideterminant approximation by the MRMP2 method. The other methods are less suitable for solving this problem. The calculated data demonstrate that the reaction proceeds via both competing pathways. Rate constant values consistent with experimental data and plausible Criegee-to-DeMore rate constant ratios have been obtained. The concerted addition of ozone to ethylene is significantly more rapid than the nonconcerted addition.