Explorations into new reaction chemistry

This Review describes the basic concepts that have guided our exploration of new chemical reactions by giving examples of results from my research group. Our strategy of carrying out research is to investigate three to four different topics at a time so we can gather as many results as possible. These may at first appear unrelated to each other but may have the potential to be united into a greater hypothesis after repeated feedback. Three scenarios from our research are presented: the "oxidative-reductive condensation reaction" devised in 1960, which after an interval of nearly 40 years brought forth the new concept of using compounds of structure Ph(2)POR as reducing reagents; the "TiCl(4)-aldol reaction" of 1973 that eventually led to the present "base-promoted aldol reaction" through a chain of ideas; and the "glycosylation reaction using fluorosugars" from 1984 which recently bloomed into "stereocontrolled glycosylation". Thus, it can be said that by reviewing what we had done before, we were able to expand on it to achieve new outcomes.     

Metallocene carbene chemistry

The Group IV bent metallocenes Cp₂M (M = Ti, Zr, Hf) were involved in carbene-related chemistry in various ways. Examples from four different areas are used to illustrate this. In situ generated Cp₂M: species exhibit some carbene-like character. They add to olefins, and their addition products can incorporate additional unsaturated organic reagents, e.g., alkyne, to form five-membered metallacycles. The high oxophilicity of the Group IV metals helps the addition of alkene-, aryne-, ²-ketone-, ²-aldehyde-, or butadiene-containing reagents to a great variety of metal carbonyl compounds to form the Fischer-type carbene complexes. The resulting zirconoxycarbene complexes have found some application in organometallic chemistry and in organic synthesis. Reactive [Cp₂M^IVR]⁺ cations can be stabilized by the addition of the Arduengo carbenes that serve as bulky two-electron donor ligands. First examples were structurally characterized. Dialkylimidazol-2-ylidenes also add to the electrophilic MX₄ compounds yielding stable trans-bis(imidazol-2-ylidene)MX₄ systems. Several examples are presented where ruthenium carbene complexes are used for carrying out catalytic olefin metathesis reactions at pendant olefinic substituents at the bent metallocenes. These reactions have led to the formation of novel bimetallic metallocene systems, as well as to new ansa-metallocenes. These catalytic reactions have helped in the current efforts to develop a functional group chemistry at the sensitive Group IV bent metallocene frameworks.     

Negative gas‐phase ion chemistry of GeH4: a quadrupole ion trap study

Gas‐phase anion/molecule reactions of germanium hydride were studied by quadrupole ion trap (QIT) mass spectrometry. Under chemical ionization (CI) conditions and with a sample pressure of about 5.0 × 10^?5 Torr, clustering reactions proceed up to the formation of Ge₅H ion clusters. With increasing cluster size, the most abundant ion species are those with the lowest content of hydrogen. Reaction sequences obtained by ion isolation were determined for primary, secondary and tertiary germane ions, and reaction enthalpies were calculated for reactions of primary ions. Ion/neutral condensation processes followed by single and double dehydrogenation are by far the most important reactions; moreover, isotope scrambling is observed for almost every reactant ion. These results are in good agreement with previously published data and indicate that germane negative ions are quite efficient in formation and growth of ionic clusters, which can be considered suitable precursors of amorphous solid hydrogenated germanium used in the semiconductor field. Copyright © 2005 John Wiley & Sons, Ltd.     

Trope theory and the ontology of chemistry

The traditional ontology within which chemistry has developed involved various versions of a general substance/attribute scheme. Recently this has been challenged by two versions of Dynamism. One version is derived from the writings of A. N. Whitehead and the other from several sources, including G. Leibniz and I. Kant. Both involve the idea of flux of actual occasions. Unlike the former scheme, the latter involves a foundation of causal powers and the energetics of field theory. The situation has been made more interesting because of the revival of trope theory, based on an ontology of particularized attributes. This notion is claimed to resolve philosophical problems about the nature of universals and of substances through the introduction of spatial and temporal sequences of tropes. While trope theory seems, at first sight, to work as an attractive alternative to substance/attribute close inspection shows that it is beset with difficulties that are more problematic that the dynamist ontology based on casual powers, dispositions and affordances.

Isomers in the chemistry of mercury coordination compounds

The coordination chemistry of mercury is an extremelybroad field, as shown by a survey covering the crystallographic and structural data of over 550 examples. About 12% of those complexes exist as isomers and are summarised and classified in this review. Included are distortion (73%), polymerisation (20.6%), coordination number (3.2%) and ligand (3.2%) isomerism. These are discussed in terms of the coordination around the mercury atoms, and correlations are drawn between donor atoms, bond distances and bond angles. Distortion isomers, differing only by the degree of distortion in the Hg — L and L — Hg — L angles, are the most common. These isomers are discussed and compared with those found in the chemistry of zinc and cadmium.      

Dynamic covalent chemistry

Dynamic covalent chemistry relates to chemical reactions carried out reversibly under conditions of equilibrium control. The reversible nature of the reactions introduces the prospects of "error checking" and "proof-reading" into synthetic processes where dynamic covalent chemistry operates. Since the formation of products occurs under thermodynamic control, product distributions depend only on the relative stabilities of the final products. In kinetically controlled reactions, however, it is the free energy differences between the transition states leading to the products that determines their relative proportions. Supramolecular chemistry has had a huge impact on synthesis at two levels: one is noncovalent synthesis, or strict self-assembly, and the other is supramolecular assistance to molecular synthesis, also referred to as self-assembly followed by covalent modification. Noncovalent synthesis has given us access to finite supermolecules and infinite supramolecular arrays. Supramolecular assistance to covalent synthesis has been exploited in the construction of more-complex systems, such as interlocked molecular compounds (for example, catenanes and rotaxanes) as well as container molecules (molecular capsules). The appealing prospect of also synthesizing these types of compounds with complex molecular architectures using reversible covalent bond forming chemistry has led to the development of dynamic covalent chemistry. Historically, dynamic covalent chemistry has played a central role in the development of conformational analysis by opening up the possibility to be able to equilibrate configurational isomers, sometimes with base (for example, esters) and sometimes with acid (for example, acetals). These stereochemical "balancing acts" revealed another major advantage that dynamic covalent chemistry offers the chemist, which is not so easily accessible in the kinetically controlled regime: the ability to re-adjust the product distribution of a reaction, even once the initial products have been formed, by changing the reaction's environment (for example, concentration, temperature, presence or absence of a template). This highly transparent, yet tremendously subtle, characteristic of dynamic covalent chemistry has led to key discoveries in polymer chemistry. In this review, some recent examples where dynamic covalent chemistry has been demonstrated are shown to emphasise the basic concepts of this area of science.     

Feedback shift register sequences versus uniformly distributed random sequences for correlation chromatography

Two alternative input sequences are commonly employed in correlation chromatography (CC). They are sequences derived according to the algorithm of the feedback shift register (i.e., pseudo random binary sequences (PRBS)) and sequences derived by using the uniform random binary sequences (URBS). These two sequences are compared. By applying the "cleaning" data processing technique to the correlograms that result from these sequences, we show that when the PRBS is used the S/N of the correlogram is much higher than the one resulting from using URBS.     

PEG- and peptide-grafted aliphatic polyesters by click chemistry

Novel aliphatic polyesters with pendent acetylene groups were prepared by controlled ring-opening polymerization and subsequently used for grafting poly(ethylene glycol) and oligopeptide moieties by the Cu(I)-catalyzed addition of azides and alkynes, a type of "click" chemistry. These aliphatic polyesters possess an acetylene graft density that can be tailored by ring-opening copolymerization of alpha-propargyl-delta-valerolactone (1) with epsilon-caprolactone. Since the mild conditions associated with the click reaction are shown to be compatible with the polyester backbone, this method is a generally useful means for grafting numerous types of functionality onto aliphatic polyesters. The amphiphilic graft polyesters prepared in this study are shown to be biocompatible by in vitro cytotoxicity evaluation, suggesting their suitability for a range of biomaterial applications.     

Supramolecular analytical chemistry

A large fraction of the field of supramolecular chemistry has focused in previous decades upon the study and use of synthetic receptors as a means of mimicking natural receptors. Recently, the demand for synthetic receptors is rapidly increasing within the analytical sciences. These classes of receptors are finding uses in simple indicator chemistry, cellular imaging, and enantiomeric excess analysis, while also being involved in various truly practical assays of bodily fluids. Moreover, one of the most promising areas for the use of synthetic receptors is in the arena of differential sensing. Although many synthetic receptors have been shown to yield exquisite selectivities, in general, this class of receptor suffers from cross-reactivities. Yet, cross-reactivity is an attribute that is crucial to the success of differential sensing schemes. Therefore, both selective and nonselective synthetic receptors are finding uses in analytical applications. Hence, a field of chemistry that herein is entitled "Supramolecular Analytical Chemistry" is emerging, and is predicted to undergo increasingly rapid growth in the near future.     

Ethylenimine chemistry

2-Methyl-N-aminoethylenimine was synthesized by the classic Wenker method and by amination of 2-methylethylenimine with hydroxylamine-O-sulfonic acid in alkaline media. NMR spectroscopy indicated the formation of exclusively the trans-inverted isomer, the pyramidal stability of the heteroatom of which, as in N-aminoethylenimine [3–5], is preserved over a broad range of temperatures. The hydrazones of N-aminoethylenimine are characterized by an appreciably lower pyramidal stability of the nitrogen than that associated with participation of its unshared electron pair in p, conjugation with the electrons of the C=N bond. The inversion barrier in the hydrazones decreases symbatically with an increase in the degree of the indicated interaction. However, the decrease is insufficient to freeze free rotation about the nitrogen-nitrogen bond up to –80.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 45–48, January, 1971.See [1] for communication VI.     

The chemistry of ethyleneimine

The reaction of N-aminoethyleneimine (I) with substituted benzenesulfonyl chlorides (II) has been studied. The main products of the heterolysis of the ring are substituted N-(-chloroethyl)benzenesulfonohydrazides (V). The structure of V has been shown by IR, UV, and PMR spectroscopy, and also by independent synthesis.For part III, see [23].     

Textural characteristics,surface chemistry and oxidation of activated carbon

Numerous researches were reviewed and interpreted to depict a comprehensive illustration of activated carbon and its behavior towards oxidation.Activated carbon as one of the most important adsorbents is tried to be described in this review paper by terms of its"Textural Characteristics"and"Surface Chemistry".These two terms,coupled with each other,are responsible for behavior of activated carbon in adsorption processes and in catalytic applications.Although as-prepared activated carbons are usually nonselective and their surfaces suffer from lack of enough reactive groups,their different aspects may be improved and developed by diverse types of modifications.Oxidation is one of the most conventional modifications used for activated carbons.It may be used as a final modification or as a pre-modification followed by further treatment.In this paper,methods of oxidation of activated carbon and other graphene-layer carbon materials are introduced and wet oxidation as an extensively-used category of oxidation is discussed in more detail.     

Textural characteristics, surface chemistry and oxidation of activated carbon

Numerous researches were reviewed and interpreted to depict a comprehensive illustration of activated carbon and its behavior towards oxidation. Activated carbon as one of the most important adsorbents is tried to be described in this review paper by terms of its "Textural Characteristics" and "Surface Chemistry". These two terms, coupled with each other, are responsible for behavior of activated carbon in adsorption processes and in catalytic applications. Although as-prepared activated carbons are usually non-selective and their surfaces suffer from lack of enough reactive groups, their different aspects may be improved and developed by diverse types of modifications. Oxidation is one of the most conventional modifications used for activated carbons. It may be used as a final modification or as a pre-modification followed by further treatment. In this paper, methods of oxidation of activated carbon and other graphene-layer carbon materials are introduced and wet oxidation as an extensively-used category of oxidation is discussed in more detail.     

Electron localization and radiation chemistry of amides

Alkylamides (such as N,N'-dimethylformamide, N,N'-diethylformamide, and N,N'-dimethylacetamide) are aprotic solvents that are widely used in organic synthesis. These polar molecules have no electron affinity, and it is believed that irradiated liquid and solid amides stabilize excess electrons as cavity-type species analogous to hydrated and ammoniated electrons. In this study, we use isotope substitution and EPR spectroscopy to demonstrate that, in frozen amides, the suspected "cavity electron" is, in fact, a solvent-stabilized monomer anion. Our observations call into question other attributions of such features in the literature, both in low temperature solids and room temperature liquids. We also provide a general scheme describing amide radiolysis, as the related amides are used as metal ion extracting agents in nuclear separations.     

The chemistry of ethyleneimine

The structure of the products of the reaction of -hydrazinoethyl hydrogen sulfate with aldehydes has been studied. In an alkaline media, the condensation products are converted into hydrazones of N-aminoethyleneimine or the corresponding azines. The structure of the cyclization products was shown by UV, IR, and PMR spectroscopy.For part IV, see [1].     

The chemistry of indoles

It has been established that when -oxonitrile arylhydrazones are boiled in glacial acetic acid substituted -carbolines are formed.It has been established that when -oxonitrile arylhydrazones are boiled in glacial acetic acid substituted -carbolines are formed.For part XIV, see [1].     

An application of neural networks in chemistry. Prediction of13C NMR chemical shifts

Basic definitions of neural networks are given in terms of oriented graphs. Partial derivatives of an objective function with respect to the weight and threshold coefficients are derived. These derivatives are very important for the adaptation process, carried out by a version of the gradient method of We neural network considered. The stability of the adapted neural network toward small changes — perturbation — of input activities is described by sensitivities. The theory is illustrated by application of simple neural networks that reflect the topology of molecules to the classification of¹³C NMR chemical shifts of secondary carbons in acyclic alkanes.     

Crystal inclusion chemistry of zinc-tetra(4-bromophenyl)porphyrin

The structural patterns of Zn(II)-tetra(4-bromophenyl)porphyrin and several of its newly prepared complexes and clathrates in the solid phase were determined by X-ray crystallography. The molecular structure of the porphyrin compound is characterized by a nearly perfect planarity of the metalloporphyrin core due to effective Zn...;Br intermolecular interactions in the crystalline lattice. The composite materials show three different kinds of interporphyrin organization, dominated to a large extent by the molecular shape, often exhibited by related tetraphenylporphyrin derivatives. These include monoclinic herringbone packing modes without any apparent involvement of the halogen atoms in specific interactions, chained interporphyrin arrangements exhibiting C-Br...; close approach, and porous layered networks of the porphyrin species revealing direct Br...;Br contacts. The latter two forms are also affected by C-H...;Br attractions. Four-, five- and six-coordination of the central zinc ion was observed, but there is no apparent correlation between the coordination number and the crystal packing type. Thermal analysis revealed the relative strength of binding of the ligand and solvate species to the porphyrin lattice. The bromophenyl-substituted porphyrin building block forms only a small number of crystalline heteromolecular materials with other components, and occurrence of the uniquely structured porous porphyrin networks is not as dominant as in the analogous chlorophenyl derivatives. Estimates of interporphyrin packing stabilization energies suggest that the stability of these layered patterns is affected primarily by dipolar attractions, which are less significant in solids containing the Br, rather than Cl, groups. Supplementary Data relating to this article have been deposited with the British Library as supplementary publication No. SUP 82200 (40 pages).     

Polymer blend complexes based on coordination chemistry

The preparation, rheology, and mechanical properties of a family of blends composed of transition-metal neutralized sulfonated ethylene-propylene-diene elastomers (S-EPDM) and styrene-4 vinylpyridine copolymers (SVP) are described. These polymeric materials contain relatively low levels of interacting groups (≤ 10 mol%), which are, however, sufficient for forming an intermolecular complex. A distinguishing characteristic of these blends is that the rheology and mechanical properties are strongly influenced by a coordination-type bonding between the transition metal and the basic nitrogen unit. As a result, markedly improved and enhanced physical properties are observed, especially when the stoichometric ratio of the interacting moieties are approached (SO/N = 1/1). This enhancement in properties is clearly exhibited in melt viscosity data, dynamic mechanical data, and thermal data. The blend morphology is also altered by complex formation, as is observed in scanning electron microscopy of the blends from which one of the ingredients was selectively extracted. At the stoichometric ratio, the blend of the olefinic elastomeric ionomer and the styrenic thermoplastic copolymer approaches a single-phase system. Such blends are otherwise completely immiscible when the coordination-type interacting groups are absent from either of the individual components. Accordingly, it was observed that nontransition-type (Na, Mg) counterions have only a marginal effect on the compatibility of these blends, as is the case in the completely unfunctionized blend components.