How metallylenes activate small molecules

We have studied the activation of dihydrogen by metallylenes using relativistic density functional theory (DFT). Our detailed activation strain and Kohn–Sham molecular orbital analyses have quantified the physical factors behind the decreased reactivity of the metallylene on going down Group 14, from carbenes to stannylenes. Along this series, the reactivity decreases due to a worsening of the back-donation interaction between the filled lone-pair orbital of the metallylene and the σ*-orbital of H₂, which, therefore, reduces the metallylene–substrate interaction and increases the reaction barrier. As the metallylene ligand is varied from nitrogen to phosphorus to arsenic a significant rate enhancement is observed for the activation of H₂ due to (i) a reduced steric (Pauli) repulsion between the metallylene and the substrate; and (ii) less activation strain, as the metallylene becomes increasingly more predistorted. Using a rationally designed metallylene with an optimal Group 14 atom and ligand combination, we show that a number of small molecules (i.e. HCN, CO₂, H₂, NH₃) may also be readily activated. For the first time, we show the ability of our H₂ activated designer metallylenes to hydrogenate unsaturated hydrocarbons. The results presented herein will serve as a guide for the rational design of metallylenes toward the activation of small molecules and subsequent reactions.

Quantum chemical analyses reveal how model metallylene catalysts activate H₂. This is the first step towards the rational design of metallylenes for the activation of small molecules and subsequent reactions.     

Reactions of Ru3(CO)12 with Diphosphenes — A New Route to 50‐Electron Ru3P2 nido‐Clusters

The reaction of the symmetric diphosphene 2, 4, 6‐(CF₃)₃‐C₆H₂‐P=P‐C₆H₂‐2, 4, 6‐(CF₃)₃ 4 with Ru₃(CO)₁₂ led to the 50‐electron Ru₃P₂ nido‐cluster Ru₃(CO)₉[μ‐P‐C₆H₂‐2, 4, 6‐(CF₃)₃]₂ 5 , which in solution at room temperature displays hindered rotation of the aromatic rings about the C(aryl)—P bonds. The structure of 5 was determined by X‐ray crystal structure analysis; its Ru₃P₂ centre forms a distorted square pyramid with one ruthenium atom at the apex. One of the two C₆H₂(CF₃)₃ groups is also appreciably distorted. Temperature‐dependent ¹⁹F NMR studies of the [A₃M₃X]₂ spin system (A = M = CF₃, X = ³¹P) of 5 indicated a rotational barrier ΔG^≠ of 82.3 kJ mol^‐1 at 141 °C. The same Ru₃P₂ core was obtained by the reaction of the unsymmetric diphosphene Mes*‐P=P‐Mes 11 with Ru₃(CO)₁₂; hindered rotation about the C(aryl)—P bonds was also observed, in this case.     

Watching photoinduced chemistry and molecular energy flow in solution in real time

Energized molecules are the essential actors in chemical transformations in solution. As the rearrangement of bonds requires a movement of nuclei, vibrational energy is often the driving force for a reaction. Vibrational energy can be redistributed within the "hot" molecule, or relaxation can occur when molecules interact. Both processes govern the rates, pathways, and quantum yields of chemical transformations in solution. Unfortunately, energy transfer and the breaking, formation, and rearrangement of bonds take place on ultrafast timescales. This Review highlights experimental approaches for the direct, ultrafast measurement of photoinduced femtochemistry and energy flow in solution. In the first part of this Review, we summarize recent experiments on intra- and intermolecular energy transfer. The second part discusses photoinduced decomposition of large organic peroxides, which are used as initiators in free radical polymerization. The mechanisms and timescales of their decarboxylation determine the initial steps of polymerization and the microstructure of the polymer product.     

Minimal number of chromatographic test parameters for the characterisation of reversed-phase liquid chromatographic stationary phases

This paper focuses on the classification or differentiation of RP-HPLC columns based on measured chromatographic properties. A chemometric study has been conducted on a published data set consisting of 85 RP-HPLC columns and on a data set consisting of 47 self-tested columns. Principal component analysis enables determination of the number of parameters necessary for a rational differentiation. The results show that reducing the number of parameters for such differentiation still allows classification of the columns just as a higher number did. It is shown that three test parameters produce a classification similar to that obtained with five parameters.     

Fuzzy theory in analytical chemistry

The concept of fuzzy theory is described in order to provide the analyst with the means for dealing with vague statements, uncertain observations or the fuzziness of human perception and interpretation, in general. In a theoretical part, basic notions of fuzzy theory are given, such as types of membership functions, operations with fuzzy sets, definitions of fuzzy numbers, points, functions, and relations, and the use of linguistic variables. The difference between fuzziness and probability is outlined. The applications section demonstrates advantages of fuzzy theory methods compared to common mathematical methods with respect to data handling for calibration of analytical methods, to classification of Chromatographie and spectroscopic patterns, to component identification and multicomponent analysis, and to designing fuzzy expert systems for selection of analytical procedures.     

Encapsulated guest molecules in the dimer of octahydroxypyridine[4]arene

Recently a new type of calix[4]arenes has been synthesized via condensation of 2,6-dihydroxypyridine and a number of aldehydes. This type of pyridine[4]arenes forms capsules consisting of two single pyridine[4]arenes. These capsules can incorporate different guest molecules, like carboxylic acids and amides in this case. We proved that the guest acids really are incorporated inside the cavity of the capsules by electrospray mass spectrometry, NMR spectroscopy, and theoretical calculations.     

The absolute configuration of peroxisomicines A1 and A2

Peroxisomicine A1 is a potentially antineoplastic compound isolated from the seeds of Karwinskia parvifolia. It is considered as a useful chemotype for the preparation of topoisomerase II targeted anticancer cells. Stereochemically, it is characterized by the presence of two stereocenters and a rotationally hindered and thus likewise stereogenic biaryl axis. In this contribution, the absolute configuration of peroxisomicine A1 and its epimer, peroxisomicine A2, was established by means of a five-step degradative procedure giving the respective R- and S-configured methyl 2-(2′-methyl-5′-oxotetrahydrofuryl)acetates. The configuration of the degradation product was obtained by means of optical rotation, ¹H NMR analysis using a chiral displacement reagent, and by experimental and quantum chemical circular dichroism (CD) investigations. Based on the results obtained here and considering our previous work on the relative configuration at centers versus axis of these compounds, peroxisomicine A1 resulted to be the P,3S,3′S-isomer and peroxisomicine A2 the P,3R,3′S-isomer.     

Structural investigation of high-valent manganese-salen complexes by UV/Vis,Raman, XANES,and EXAFS spectroscopy

XANES and EXAFS spectroscopic studies at the Mn-K- and Br-K-edge of reaction products of (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) chloride ([(salen)Mn(III)Cl], 1) and (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) bromide ([(salen)Mn(III)Br], 2) with 4-phenylpyridine N-oxide (4-PPNO) and 3-chloroperoxybenzoic acid (MCPBA) are reported. The reaction of the Mn(III) complexes with two equivalents of 4-PPNO leads to a hexacoordinated compound, in which the manganese atom is octahedrally coordinated by four oxygen/nitrogen atoms of the salen ligand at an average distance of approximately 1.90 A and two additional, axially bonded oxygen atoms of the 4-PPNO at 2.25 A. The oxidation state of this complex was determined as approximately +IV by a comparative study of Mn(III) and Mn(V) reference compounds. The green intermediate obtained in reactions of MCPBA and solutions of 1 or 2 in acetonitrile was investigated with XANES, EXAFS, UV/Vis, and Raman spectroscopy, and an increase of the coordination number of the manganese atoms from 4 to 5 and the complete abstraction of the halide was observed. A formal oxidation state of IV was deduced from the relative position of the pre-edge 1s-->3d feature of the X-ray absorption spectrum of the complex. The broad UV/Vis band of this complex in acetonitrile with lambda(max)=648 nm was consistent with a radical cation structure, in which a MCPBA molecule was bound to the Mn(IV) central atom. An oxomanganese(V) or a dimeric manganese(IV) species was not detected.