On the growth of percolation clusters: The effects of time correlations

We discuss the effects of the time correlations in the choice of growth sites for percolation clusters in two dimensions. To this end, we study two well-defined models: (i) FIFO (First-In, First-Out), in which the next-cluster growth site is theoldest, and (ii) FILO (First-In, Last-Out), where the next cluster growth site to be chosen is thenewest. We find that FIFO and FILO have dramatically differentkinetic exponents, even though thestatic exponents are the same (viz., percolation exponents). We find that the percolation thresholdp _c is analogous to the point of a linear polymer, and we develop the corresponding tricritical point scaling relations.Dedicated to B. Mühlschlegel on the occasion of his 60th birthday     

Modulation des flammenspektrometrischen Signals mittels intermittierender Probenzufuhr zur Flamme

Zusammenfassung An Stelle eines Choppers wird zur Modulation des flammenspektrometrischen Signals die Probenflüssigkeit periodisch der Flamme zugeführt (intermittierende Zerstäubung). Es wird zunächst über die beobachtete Eigenmodulation der Zerstäubung berichtet und danach über die intermittierende Zerstäubung mit Frequenzen bis zu 50 Hz. Anschließend wird an Hand von Beispielen gezeigt, daß sich die intermittierende Zerstäubung als besonders vorteilhaft in der Absorptions-Flammenspektrometrie erweist. Wird das Gleichlicht des Hintergrundstrahlers mittels der intermittierenden Zerstäubung in der Flamme moduliert und ein Wechselstromverstärker verwendet, so fallen der 0- und 100%-Durchlässigkeitspunkt zusammen. Bei der Registrierung über die Wellenlänge werden dann nur solche Linien angezeigt, welche in der Flamme das eingestrahlte Licht absorbieren.

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Summary For modulating the flame spectrometric signal without using a chopper the sample is introduced into the flame periodically (intermittent atomisation). First, the observed self-modulation of the atomisation is described and subsequently the intermittent atomisation with frequencies up to 50 cps. Some examples demonstrate that intermittent atomisation proves to be especially advantageous in absorption flame spectrometry. When modulating the light of the dc-operated line source by means of intermittent atomisation and using ac-amplification of the modulated signal the 0- and 100%-transmittance points of the transmittance scale are the same. When scanning over the wave length only such lines are detected which absorb the light of the background source.

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Der Fa. Siemens-Reiniger Werke AG., Erlangen, und insbesondere Herrn Ing. Engel danken wir auch an dieser Stelle für die leihweise Überlassung des Flüssigkeitsstrahloscillographen Cardirex 31 B. — Herrn K. RÜdiger danken wir für die wertvollen Hinweise und für die Durchführung der Werkstattarbeiten.     

Synthesis of benzopyran derivatives,XV Preparation of arylsulfonyloxy-2,2-dimethyl-2H-chromenes

Summary Arylsulfonyloxy-2,2-dimethyl-2H-chromenes (26–35) have been synthesized by reduction of arylsulfonyloxy-2,2-dimethyl-4-chromanones (6–15) followed by dehydration.

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Synthese von Benzopyranderviaten. 15. Mitt.: Darstellung von Arylsulfonyloxy-2,2-dimethyl-2H-chromenen

Zusammenfassung Reduktion von Arylsulfonyloxy-2,2-dimethyl-4-chromanonen (6–15) und anschließende Dehydratisierung liefert Arylsulfonyloxy-2,2-dimethyl-2H-chromene (26–35).

     

Übergangsmetall-methylen-komplexe: LVI. Organoruthenium-komplexe mit offenkettigen und carbocyclischen alkyliden-brücken: Synthese,konstitution, isomerie,protonierung und thermolytischer abbau

The eighteen new μ-alkylidene ruthenium complexes 5a–r and 5t are very easily and cleanly obtained along the diazoalkane or the hydrazone routes that involve treatment of the dinuclear, metal-metal doubly bonded precursor compound [(η⁵-C₅H₅)Ru(μ-NO)]₂ (3) either with the diazoalkanes oxidizing agent (e.g., MnO₂), with the respective hydrazones. Similarly, sulfur dioxide adds cleanly to the RuRu double bond of 3, thus giving the complex (μ-SO₂)[(η⁵-C₅H₅)Ru(NO)]₂ (5s). Regardless of the nature of the carbene bridge ligands, the dimetallacyclopropanes exhibit, in contrast to their iron analogues, exclusively terminal nitrosyl ligands. cis/trans-Isomerism with predominating amounts of the trans-isomers is observed for the derivatives that display unsymmetrically substituted carbene bridges.Treatment of the μ-methylene- and μ-ethylidene complexes (μ-CH₂)[(η⁵-C₅H₅)Ru(NO)]₂ (5a) and (μ-CHCH₃)[(η⁵-C tetrafluoroboric acid or trifluoromethanesulfonic acid in diethyl ether yields, at ambient temperature, quantitatively the ionic complexes 6a,b and 7a,b, respectively, which were shown by ¹H NMR spectroscopy to contain metal-metal bridging hydrogen functionalities. The reaction of hydrogen bromide with 5a under the same conditions gives the neutral bromo(methyl) complex 6d. This latter compound results from the isolable ionic intermediate of composition [(μ-CH₂)(μ-H){(η⁵C₅H₅)Ru(NO)}₂]⁺Br^? (6c), which reaction stems from the nucleophilicity of the halide ion present in 6c.     

Multiple Bonds between Transition Metals and “Bare” Main Group Elements: Links between Inorganic Solid State Chemistry and Organometallic Chemistry

The last two decades have seen a dramatic development in the study of metal-metal multiple bonds, particular successes being recorded in the field of organometallic chemistry. Syntheses designed to produce novel transition metal complexes with single, double, triple and quadruple metal-metal bonds occupy a most important place in such research, as also do reactivity studies. A striving to establish general principles has provided much of the motivation for such work, but one less obvious goal—the commercial application of the catalytic properties of metal-metal multiple bonding systems, in the medium and long term—should not be overlooked. All aspects of the investigations of metal-metal multiple bonds also apply to a particular class of compound that has, however, enjoyed little lime-light and thus deserves the present review: complexes with multiple bonds between transition metals and substituent-free (“bare”) main group elements. Although based mostly on accidental discoveries, the few noteworthy examples are now beginning to unfold general concepts of synthesis that are capable of being extended and thus are deserving of exploitation in preparative chemistry. The availability of further structural patterns exhibiting multiple bonds between transition metals and ligand-free main group elements might enable preparative organometallic chemistry to expand in a completely new direction (for instance by the stabilizing or activation of small molecules at the metal complex). This essay discusses the chemistry of complexes of bare carbon, nitrogen, and oxygen ligands (carbido-, nitrido-, and oxo-complexes) and their relationships to higher homologues from both a synthetic and a structural point of view.     

MM3 parametrization of four‐ and five‐coordinated rhenium complexes by a genetic algorithm—Which factors influence the optimization performance?

Genetic algorithms (GA) were used to solve one of the multidimensional problems in computational chemistry, the optimization of force field parameters. The correlation between the composition of the GA, its parameters (p(c), p(m)) and the quality of the results were investigated. The composition was studied for all combinations of a Simple GA/Steady State GA with a Roulette Wheel/Tournament Selector using different values each for crossover (0.5, 0.7, 0.9) and mutation rates (0.01, 0.02, 0.05, 0.10, 0.20). The results show that the performance is strongly dependent on the GA scheme, where the Simple GA/Tournament Selector yields the best results. Two new MM3 parameters were introduced for rhenium compounds with coordination number four (204) and coordination number five (205), the formal oxidation states of rhenium ranging from +V to +VII. A manifold of parameters (Re-C, N, O, S) was obtained by using a diverse set of CSD structures. The advantage of the GA vs. UFF calculations is shown by comparison of several examples. The GA optimized parameters were able to reproduce the geometrical data of the X-ray structures.