bluuebunny/crossref_metadata_2025 huggingface dataset:
Keatifitas dan Inovasi Pembelajaran dalam Pengembangan Kreatifitas Melalui Imajinasi, Musik, dan Bahasa
Authors: Rahayu Nanik , Putri H Saniyya , Masitha Nunlehu  , Mia Sumiani Madi  , Khalid Nurbani
Published: March 2024

Creativity and innovation is a person's ability to develop or to generate new ideas or ideas that are useful for solving problems in everyday life. Children's creativity is very important to be developed from an early age. Several ways to develop creativity and also learning innovation in early childhood can be done through imagination, music and language. In creativity through imagination, children are invited to imagine, imagine and also demonstrate something that they think. By using several objects, children can imagine objects or themselves to be different figures. That way the development of children in creativity will be optimally stimulated. In musical creativity, children are invited to use objects or items that are around them in various ways so that they can produce sounds or tones which can then be combined with lyrics so that they become a rhythmic song. The development of creativity in the development of music can not only improve the artistic aspect, but also the child's thinking power of imagination that describes an object that becomes a musical instrument. In language creativity, children are invited to express their ideas or ideas by expressing them into an opinion. The development of children's creativity can be developed in various ways, of course through fun activities for children so that children can feel comfortable and can optimize their development. This article aims to describe the development of children's creativity and innovation through imagination creativity, musical creativity, and language creativity. The method used for data collection is in the form of a literature study, namely a method that can study various reference books and similar previous research results.

 

Keywords: Learning Creativity, Imagination Creativity, Music Creativity, Language Creativity
Reviews
Authors: Arvidsson Alf , Ballantyne Patricia H. , Eriksson Karin L. , Mátéffy Attila , Strand Karin , Hellqvist Eva Kjellander , Nordström Marika , Dimitrova Birgitta Englund , Pripp Oscar , Thedens Hans-Hinrich , Hoppu Petri , Lundberg Dan
Published: March 2024

Recensioner av:

Cultural Mapping and Musical Diversity av Britta Sweers & Sarah M Ross (eds).
Dance Legacies of Scotland: The True Glen Orchy Kick av Mats Melin & Jennifer Schoonover
Folklore Revival Movements in Europe post 1950: Shifting Contexts and Perspectives av Daniela Stavělová och Theresa Jill Buckland (red.)
Foundations of Hungarian Ethnochoreology: Selected Papers of György Martin av János Fügedi, Colin Quigley, Vivien Szőnyi & Sándor Varga (eds.)
Harpe og sverd: Litteraturhistoriske essay om den norske balladen av Olav Solberg
Lyssna på musik: Upplevelser, mening, hälsa av Lars Lilliestam
Dissertation - Music in International Development: The Experience of Concerts Norway (2000–2018) av Solveig Korum
Song Translation: Lyrics in Contexts av Johan Franzon, Annjo K. Greenall, Sigmund Kvam och Anastasia Parianou (red)
Sounds of Migration: Music and migration in the Nordic countries av Owe Ronström & Dan Lundberg (red.)
Visions and Traditions: Knowledge Production and Tradition Archives av Lauri Harviahti, Audun Kjus, Susanne Österlund-Pötzsch, Fredrik Skott & Rita Treija (eds.)
Waltzing Through Europe: Attitudes towards Couple Dances in the Long Nineteenth Century av Egil Bakka, Theresa Jill Buckland, Helena Saarikoski & Anne von Bibra Wharton (eds.)
Dissertation - Wind and Wood: Affordances of Musical Instruments: The Example of the Simple-System flute av Markus Tullberg
Timing-Sound Interactions
Authors: Johansson Mats
Published: March 2024

This article reports on a study of concepts and practices of microrhythm among skilled performers of traditional Scandinavian fiddle music, particularly the so-called springar tradition which features non-isochronous and variable beats and subdivisions within a triple meter framework. In this context, microrhythm refers to the overall shaping of musical events at the micro level, encompassing both timing (temporal placement and duration) and sound (shape/envelope, timbre and intensity). A particular focus is to explore how these musical features interact – as opposed to treating timing and sound separately – and how timing-sound interactions in turn are understood in terms of groove-forming elements. The study consisted of semi-structured interviews with four expert musicians, which have been transcribed and coded for key themes and concepts. Subsequently, these data were complemented by analyses of relevant musical segments. The interviews focused on the defining features of a good groove, and how aspects of sound are envisaged to affect aspects of rhythm and timing, and vice versa. It was found that groove is largely conceptualised in terms of movement and embodiment; that musical features (timing, accentuation, ornamentation, tone production) are seen to interact and overlap, suggesting a multi-parametrical concept of groove; and that melodic-rhythmic variation is an important groove-forming element. The interviews also revealed a strongly practice-oriented perspective on performance and aesthetics in which musical concepts are tightly integrated with their associated sound-producing movements (bowing, fingering, foot tapping).
Music as an expression of Jewishness in contemporary Poland
Authors: Muszkalska Bożena
Published: March 2024

Over half a century after the Holocaust, in Eastern European countries where the Jewish community remained only a small part of the population, products of Jewish culture (or what is perceived as Jewish culture), including music, have become vital components of the popular public domain. In Poland, there are festivals and concerts of Jewish music, more and more records with this music, Jewish museums, and renovated Jewish districts, with Jewish cuisine, and music that are offered to tourists visiting Poland as the main attractions. They attract enthusiastic – and often non-Jewish – crowds. I consider how non-Jews involved in this movement in Poland perceive and implement Jewish culture, why they do it, how much it involves the recovery of Jewish heritage, and how this represents the musical culture of Jews in museums and at events organized for tourists. I also consider the relation of non-Jews as a majority group to Jews as a minority group, as well as the impact of the musical actions of the former on the musical culture of the latter. The article is based on field research and observations I have made during more than twenty years, both among the remaining Jews in Poland and in mixed or non-Jewish communities where music perceived as Jewish is promoted.
Performing in Sweden
Authors: Ålander Jonas
Published: March 2024

This study investigates how an Immigrant identification affects musicians’ possibilities to perform in Sweden. This is investigated through a discourse theoretical analysis of interviews with seven musicians. The analysis shows several intersections where an Immigrant identification has affected the informants’ lives and careers, hence contributed to shaping their working conditions. For example, the Immigrant identification can be related to the informants’ possibilities of being granted access to the stage. Several informants have experienced discrimination because of their appearances and as a result taken preemptive measures to fit envisioned expectations by changing name or by avoiding performing at certain music venues. The Immigrant identity is also shown to be closely connected with music genres and ideas about authenticity, which limits the availability of musical pathways. This occurs, for example, when an artist considers which genre to engage in because of how the genre relates to an Immigrant identity. The study shows that when musicians’ careers coincide with an Immigrant identification, participative conditions often prove immutable and hegemonic. There are however expressions of change and resistance toward prevailing participative conditions among the informants, but they do not perceive these conditions to be given enough attention in society or by the music industry.
Inkorporacja wybrzeża Boliwii do systemu-świata według teorii Immaneula Wallersteina
Authors: Roczon Mateusz
Published: March 2024

Celem niniejszego artykułu jest przedstawienie społeczno-gospodarczych zjawisk, jakie zaszły w II połowie XIX wieku w nadmorskiej prowincji Boliwii i jej podboju przez Chile jako przykładu inkorporacji obszaru zewnętrznego do systemu-świata. Autor twierdzi, że przed powstaniem górnictwa azotanów na omawianym obszarze był on obszarem efektywnie zewnętrznym wobec kapitalistycznej gospodarki-świata. Dalsze przemiany gospodarcze, demograficzne i polityczne są analizowane jako wypełnienie 3 warunków inkorporacji postulowanych przez Immanuela Wallersteina, – odpowiednio: powstanie Compañía de Salitres y Ferrocarril de Antofagasta jako skrajna forma wytworzenia podmiotów produkujących na wielką skalę, migracja chilijska jako zapewnienie niezbędnej siły roboczej i chilijski podbój jako przekształcenie struktury politycznej obszary zgodne z jego nową peryferyjną rolą i potrzebami gospodarki-świata.
Curd, seed yield and disease resistance of cauliflower are enhanced by oligosaccharides
Authors: Rajib Md. Mijanur Rahman , Sultana Hasina , Gao Jin , Wang Wenxia , Yin Heng
Published: March 2024

Background

Oligosaccharides have been demonstrated as promoters for enhancing plant growth across several crops by elevating their secondary metabolites. However, the exploration of employing diverse oligosaccharides for qualitative trait improvements in cauliflower largely unknown. This study was intended to uncover the unexplored potential, evaluating the stimulatory effects of three oligosaccharides on cauliflower’s curd and seed production.

Methods

Two experiments were initiated in the early (15 September) and mid-season (15 October). Four treatments were implemented, encompassing a control (water) alongside chitosan oligosaccharide (COS 50 mg.L–1) with a degree of polymerization (DP) 2–10, oligo galacturonic acid (OGA 50 mg.L−1) with DP 2–10 and alginate oligosaccharide (AOS 50 mg.L−1) with DP 2–7.

Results

Oligosaccharides accelerated plant height (4–17.6%), leaf number (17–43%), curd (5–14.55%), and seed yield (17.8–64.5%) in both early and mid-season compared to control. These enhancements were even more pronounced in the mid-season (7.6–17.6%, 21.37–43%, 7.27–14.55%, 25.89–64.5%) than in the early season. Additionally, three oligosaccharides demonstrated significant disease resistance against black rot in both seasons, outperforming the control. As a surprise, the early season experienced better growth parameters than the mid-season. However, performance patterns remained more or less consistent in both seasons under the same treatments. COS and OGA promoted plant biomass and curd yield by promoting Soil Plant Analysis Development (SPAD) value and phenol content. Meanwhile, AOS increased seed yield (56.8–64.5%) and elevated levels of chlorophyll, ascorbic acid, flavonoids, while decreasing levels of hydrogen per oxide (H2O2), malondialdehyde (MDA), half maximal inhibitory concentration (IC50), and disease index. The correlation matrix and principal component analysis (PCA) supported these relations and findings. Therefore, COS and OGA could be suggested for curd production and AOS for seed production in the early season, offering resistance to both biotic and abiotic stresses for cauliflower cultivation under field conditions.
Characterization of ferromagnetic and antiferromagnetic systems using nitrogen-vacancy center relaxometry
Authors:   , Cabezón Heitzer Ricardo Javier
Published: March 2024

Relaxometry with nitrogen-vacancy (NV) centers in diamond is an innovative and non-invasive technique that has been increasingly used for characterizing magnetic materials. Because of their exceptional quantum coherence and capability to be manipulated optically, it is possible to measure their relaxation time and, from this quantity, probe physical characteristics of the environment. This technique is the so-called called relaxometry. During the last few years, NV centers have been used for measuring magnetic properties in ferromagnetic materials, and a few times for antiferromagnetic systems with easy-axis anisotropy.In this work, we develop a complete theoretical description of NV center relaxometry for several types of magnetic materials (ferromagnetic and antiferromagnetic systems), we indicate what physical parameters can be measured in each situation, when this technique will experimentally work, and how it depends on the sample anisotropy. We found that relaxation rates using ferromagnetic systems peak at certain values of the external magnetic field, where both NV center and sample resonate simultaneously, something that does not happen when using antiferromagnets because of their high resonance frequency. In this way, NV center relaxometry allows us to extract information about the spin waves of the system. Finally, we discuss prospects to non-intrusively probe magnetic properties and phase transitions in ferrimagnetic systems, in triangular-lattice antiferromagnets, such as Cs2CuCl4 and in 2D materials.
Speciation of Phytate Ion in Aqueous Solution. Trimethyltin(IV) Interactions in Self Medium
Authors: Crea Francesco , Crea Pasquale , Milea Demetrio , Porcino Nunziatina , Sammartano Silvio
Published: July 2007

In this paper the results of a potentiometric (ISE‐[H+] glass electrode) investigation at t = 25 °C on the complexing ability of phytate towards trimethyltin(IV) (tmt) and on the acid‐base properties of tmt at high metal concentration (0.050 and 0.075 mol L‐1) are reported. First we determined the hydrolytic constants of tmt in aqueous solution without further addition of background salt (self medium); in these experimental conditions we verified the formation of the following hydrolytic species: tmt(OH)0, tmt(OH)2‐ and the binuclear species (tmt)2(OH)+. Successively, we studied the complex formation constants obtained from the interaction of phytate anion with tmt in the same experimental conditions of hydrolytic measurements; the speciation model obtained takes into account several polynuclear species (tmtH5Phy6‐; tmt2H5Phy5‐; tmt3H4Phy5‐; tmt3H5Phy4‐; tmt4H6Phy2‐; tmt5HPhy6‐). A comparison with literature data is reported too.
Analysis of Mural Paintings in Istria
Authors: Mazzocchin G.A. , Rudello D. , Maraković N. , Marić I.
Published: July 2007

Fragments of wall paintings from Istria, coming from the Basilica of Guran near Vodnjan, from the cemeterial Church of Saint Simeon in Guran and from the Benedictine monastery of Santa Maria Alta near Bale were studied.

The analytical instrumental techniques used were Optical Microscopy, Scanning Electron Microscopy equipped with an EDS microanalysis detector, X Ray diffraction, FTIR infrared Spectroscopy and Raman Spectroscopy.

Red and yellow pigments used in Guran and Bale have bean derived from red and yellow istrian bauxites, as already demonstrated for works from 11th to 15th century.

The blue pigment found in the paintings of the Bale Chapel is a lapislazzuli blue; this fact confirms the literature data referring to the period from 11th to the 16th century.

The materials and pigments used at Bale and Guran fit with the Istrian tradition and history of painting going back to the first Carolingian period.
A Model to Predict the Steady‐State Concentration of Hydroxyl Radicals in the Surface Layer of Natural Waters
Authors: Minero Claudio , Lauri Vittorio , Maurino Valter , Pelizzetti Ezio , Vione Davide
Published: July 2007

A model was developed to predict the steady‐state [˙OH] in the surface layer of natural waters as a function of nitrate, inorganic carbon (IC) and dissolved organic matter (DOM). The parameter values were studied in the range detected in shallow high‐mountain lakes, to which the model results are most relevant. Calculations indicate that [˙OH] increases with increasing nitrate and decreasing IC, and conditions are also identified where [˙OH] is directly proportional, inversely proportional or independent of DOM. Based on the model results it is possible to predict the half‐life time, due to reaction with ˙OH, of given dissolved compounds, including organic pollutants, from the water composition data.
Seasonal and Water Column Trends of the Relative Role of Nitrate and Nitrite as *OH Sources in Surface Waters
Authors: Vione Davide , Minero Claudio , Maurino Valter , Pelizzetti Ezio
Published: July 2007

Based on literature data of sunlight spectrum, photolysis quantum yields, and absorption spectra, the relative role of nitrite and nitrate as *OH sources in surface waters was assessed, and its dependence on the season and the depth of the water column studied. In the majority of surface water samples (river, lake and seawater) nitrite is expected to play a more important role as *OH source compared to nitrate, in spite of the usually lower [NO2‐] values. Interestingly, under the hypothesis of a constant ratio of the concentrations of nitrate and nitrite (to be corrected later on for the actual concentration ratio in a given sample), the relative role of nitrite compared to nitrate would be minimum in summer, at noon, in the surface layer of natural waters. Any decrease in the sunlight intensity that can be experienced in the natural environment (different season than summer, water column absorption, time of the day other than the solar noon), with its associated influence on the sunlight spectrum, would increase the relative role of nitrite compared to nitrate.
The Formal Redox Potential of the Ti(IV, III) Couple at 25 °C in 1 M HCl 2 M NaCl Medium
Authors: Amorello Diana , Gambino Vincenzo , Romano Vincenzo , Zingales Roberto
Published: July 2007

The formal redox potential of the Ti(IV, III) couple has been determined at 25 °C in 1 M HCl, 2 M NaCl aqueous medium, by emf measurements of a junction‐free cell with glass and mercury electrodes. Ti(III) and Ti(IV) concentrations were changed by controlled electrolysis. The mean value of the searched formal potential, in a large range of total titanium concentration, is 9 ± 1 mV against the molar hydrogen electrode in the same ionic medium.
Simultaneous Spectrophotometric Determination of Phosphate and Silicate by Using Principal Component Artificial Neural Network
Authors: Zarei Kobra , Atabati Morteza , Nekoei Mehdi
Published: July 2007

A very sensitive, simple and selective spectrophotometric method for simultaneous determination of phosphate and silicate based on formation of phospho‐ and silicomolybdenum blue complexes in the presence of ascorbic acid is described. Although the complexes of phosphate and silicate with reagent in the presence of ascorbic acid show a spectral overlap, they have been simultaneously determined by principal component artificial neural network (PC‐ANN). The PC‐ANN architectures were different for phosphate and silicate. The output of phosphate PC‐ANN architecture was used as an input for silicate PC‐ANN architecture. This modification improves the capability of silicate PC‐ANN model for prediction of silicate concentrations. The linear range was 0.01‐3.00 μg mL‐1 for phosphate and 0.01‐5.00 μg mL‐1 for silicate. Interference effects of common anions and cations were studied and the proposed method was also applied satisfactorily to the determination of phosphate and silicate in detergents.
A Novel Wire‐Type Lead‐Selective Electrode Based on Bis (1'‐Hydroxy‐2'‐Acetonaphthone)‐2,2'‐Diiminodiethylamine
Authors: Pilehvari Zahra , Yaftian Mohammad Reza , Rayati Saeed , Parinejad Massoumeh
Published: July 2007

The preparation of a lead‐selective electrode based on bis(1'‐hydroxy‐2'‐acetonaphthone)‐2,2'‐diiminodiethylamine (L) as sensing material is reported. The plasticized PVC membrane containing 30% PVC, 67% ortho‐nitrophenyloctylether (NPOE) and 3% ionophore L was directly coated on a graphite rod. This electrode exhibits a nearly Nernstian slope of 27.8±0.2 mV decade‐1 over a concentration range 10‐6−10‐2 M with a detection limit of 4.0×10‐7 M. The response time of the electrode was found to be <20 s. The potential of the sensor was independent on pH variations in the range 5‐7. The selectivity of the electrode towards lead ions over Na+, K+, Ag+, Ca2+, Sr2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, La3+, Sm3+ and Er3+ ions was investigated. The prepared electrode was successfully used as an indicator for titration of a lead solution with a standard solution of EDTA. The applicability of the sensor for Pb2+ measurement in various synthetic and real samples has been also demonstrated.
Adsorption of Toxic Metals by Natural and Modified Clinoptilolite
Authors: Orhan Yüksel , Kocaoba Sevgi
Published: July 2007

The chromium, cobalt and lead removal from aqueous solution by natural and modified zeolites was examined by using a batch‐type method. Clinoptilolite samples used in this study were supplied from Bigadiç, Turkey. All samples were modified with HNO3 or NaOH to improve the adsorption capacity for heavy metals. The removal efficiencies and kinetics of heavy metals such as chromium, cobalt and lead on natural and modified zeolites were determined. The effects of the initial metal concentration on the removal percentage of heavy metal ions were studied. Freundlich and Langmuir isotherm constants and correlation coefficients were found and the equilibrium process was described by the Freundlich isotherm. The adsorption kinetic was tested and then it indicates the process to be diffusion controlled.
Male parenting and response to infant stimuli in the common marmoset (Callithrix jacchus)
Authors: Zahed S.R. , Prudom S.L. , Snowdon C.T. , Ziegler T.E.
Published: July 2007

Callithrix jacchus infants are raised in complex family environments where most members participate in rearing the young. Many studies examining male parental behavior have focused on the carrying of infants with observations made within the family context. However, interference from family members can make it difficult to assess the father's motivation to care for infants. Our goals were to develop a testing paradigm for determining an individual's response to infant stimuli separate from family influences, compare a male's motivation to respond to an infant stimulus outside the family with his paternal behavior within the family, to compare responses to infant stimuli of parentally experienced versus inexperienced males and finally to develop a reproducible and standardized method of testing male responsiveness to infant stimulus that could serve to evaluate hormonal manipulations. Fifteen experienced common marmoset fathers were evaluated using three different measures of parental behavior: (1) instantaneous scan sampling, (2) continuous focal sampling in the family, and (3) continuous focal sampling of males presented with four infant stimuli: familiar and unfamiliar infants, familiar and unfamiliar infant vocalizations. Six parentally inexperienced males (non‐fathers) served as controls. Males that carried the most in the family were typically the same males that responded most to the infant vocalization tests. Experienced fathers did not differ in their latency to enter the stimulus cage for any of the four infant stimuli response tests while inexperienced males took significantly longer to enter the stimulus cage. In addition, fathers expressed a greater frequency of infant‐directed behavior than did the inexperienced males during the unfamiliar infant and unfamiliar vocalization tests. These studies show that experienced male marmosets are highly motivated to interact with infant stimuli and that there is interindividual variability in response to infant vocalizations. Testing males outside of the family allows for a clear assessment of male's interest in infant stimuli in both parentally experienced fathers and inexperienced males. Am. J. Primatol. 70:84–92, 2008. © 2007 Wiley‐Liss, Inc.
Zur möglichen Rolle des protonengekoppelten Elektronentransfers (PCET) bei der Oxidation von Wasser durch das Photosystem II
Authors: Meyer Thomas J. , Huynh My Hang V. , Thorp H. Holden
Published: July 2007

Alle höheren Lebensformen nutzen Sauerstoff als primäre Energiequelle. Dieser Sauerstoff entsteht aus Wasser mithilfe von Sonnenlicht in Photosynthese‐Membranen. Die Absorption von Licht im Photosystem II (PSII) grüner Pflanzen aktiviert den Elektronentransfer im Sauerstoff entwickelnden Komplex (OEC). Der Mechanismus der Wasseroxidation durch den OEC ist ein wichtiges Forschungsgebiet. Die Verfügbarkeit neuer Proteinstrukturen dank Röntgenkristallographie und EXAFS sowie die Resultate vielzähliger experimenteller und theoretischer Studien bilden nun die Grundlage für einen Vorschlag, wie Wasser am OEC oxidiert werden könnte. Eine Folge lichtgetriebener Reaktionen, die einen gekoppelten Elektronen‐Protonen‐Transfer (EPT) nutzen, könnte der Schlüssel zur Wasseroxidation sein. Werden diese Reaktionen mit einem Transport von Elektronen über große Entfernungen (über sequenzielle lokale Protonenübertragungen) kombiniert, lässt sich der OEC als komplexe Struktur betrachten, die “für Protonen geschaltet” wird.
Kontrollierte Freisetzung flüchtiger Verbindungen unter milden Reaktionsbedingungen: von der Natur zu Alltagsprodukten
Authors: Herrmann Andreas
Published: July 2007

Flüchtige organische Verbindungen wirken in der Natur als Botenstoffe zur Kommunikation zwischen verschiedenen Spezies und finden zudem oft Anwendung als Aromen oder Duftstoffe, wobei die Dauer der Geruchswahrnehmung zumeist begrenzt ist. Dies führte zur Entwicklung von Proparfümen – idealerweise nichtflüchtigen, geruchslosen Duftstoffvorstufen, die aktive flüchtige Verbindungen unter Spaltung einer kovalenten Bindung freisetzen. Eine begrenzte Zahl von Reaktionsbedingungen, z. B. Hydrolysen, Temperaturschwankungen sowie die Wirkung von Licht, Sauerstoff, Enzymen oder Mikroorganismen, ermöglicht die Freisetzung vielzähliger Verbindungen. Dieser Aufsatz thematisiert die kontrollierte chemische Freisetzung von Duftstoffen und bespricht auch Hürden wie die Stabilität der Duftstoffvorstufen und einige Aspekte ihrer Giftigkeit und Biokompatibilität. Da dieselben Systeme gleichermaßen in verschiedenen Forschungsbereichen verwendet werden können, beleuchtet dieser Aufsatz auch die kontrollierte Freigabe leichtflüchtiger Substanzen im Allgemeinen.
Crowd motion capture
Authors: Courty N. , Corpetti T.
Published: July 2007

In this paper a new and original technique to animate a crowd of human beings is presented. Following the success of data‐driven animation models (such as motion capture) in the context of articulated figures control, we propose to derivate a similar type of approach for crowd motions. In our framework, the motion of the crowds are represented as a time series of velocity fields estimated from a video of a real crowd. This time series is used as an input of a simple animation model that ‘advect’ people along this time‐varying flow. We demonstrate the power of our technique on both synthetic and real examples of crowd videos. We also introduce the notions of crowd motion editing and present possible extensions to our work. Copyright © 2007 John Wiley & Sons, Ltd.
Bildung diastereomerer Zirconiooxycarbenkomplexe durch Umsetzung von Bis(tert‐butyl‐Cp)2Zr(butadien) mit Hexacarbonylowolfram
Authors: Erker Gerhard , Lecht Rainer , Sosna Friedrich , Uhl Sonja , Tsay Yi‐Hung , Krüger Carl , Grondey Hiltrud , Benn Reinhard
Published: July 2007

Die Reaktion von (η4‐Butadien)bis(η‐tert‐butylcyclopentadienyl)‐zirconium (95:5‐s‐cis‐/s‐trans‐5‐Gleichgewichtsgemisch) mit Hexacarbonylwolfram liefert den Zirconiooxycarbencomplex (6), der in der Raumgruppe P1 kristallisiert (Röntgenstrukturanalyse). Aufgrund des chiralen zentralen metallacyclischen Ringsystems und der chiralen Vorzugskonformation des Cp‐substituierten gewinkelten Metallocensystems werden diastereoisomere Zirconiooxycarbenkomplexen 6 und 6′ gebildet. Röntgenstrukturanalyse und 13C‐CP/MAS‐Spektrum deuten auf das Vorliegen eines 80:20‐Gemisches dieser diastereomeren Carbenkomplexe im Festkörper hin. Die temperaturabhängigen NMR‐Spektren des Carbenkomplexes in Lösung werden mit einem Gleichgewicht der Diastereomeren interpretiert.
Ladungstrennung auf molekularer Basis: Chemoselektivität, Regio‐ und Stereoselektivität der CC‐Verknüpfung als Sonden für Elektronentransfer‐Prozesse
Authors: Aurbach Irmgard , Ponti Pier Paolo , Salbeck Erika , Schmuck Heike , Daub Jörg
Published: July 2007

Enolate können mit Carbonylverbindungen nach einem polaren Mechanismus oder einem Mechanismus mit SET (single‐electron transfer)‐Teilschritten reagieren. Die Umsetzungen von Lithium‐8‐(dimethylamino)heptafulven‐8‐olat (1) mit Iodmethan und mit den Carbonylverbindungen Benzaldehyd (2a), Benzophenon (2b), Phenylglyoxylsäure‐methylester (2c), Benzil (2d) und 4‐Nitrobenzaldehyd (2e) werden unter diesem Gesichtspunkt untersucht. Die Struktur und die Verteilung der aus konkurrierenden Reaktionsabläufen entstehenden Verbindungen dienen der mechanistischen Diskussion. Die Chemoselektion führt entweder zur oxidativen Dimerisierung des Heptafulvens 1 bzw. Reduktion der jeweiligen Carbonylverbindung oder zur „aldolartigen”︁ CC‐Verknüpfung. Beide Reaktionswege enden bei Gemischen stereoisomerer und regioisomerer Verbindungen. Die Beteiligung von Einelektronübertragungsschritten folgt zweifelsfrei aus der Produktzusammensetzung. Eine Korrelation zwischen dem Reduktionspotential der Carbonylverbindungen und dem Produktspektrum wird gefunden.
[Tetra(2,3‐pyrido)porphyrazinato]eisen(II)‐Verbindungen mit Isocyaniden als axialen Liganden
Authors: Hanack Michael , Thies Rüdiger
Published: July 2007

Aliphatische und aromatische einzähnige Isocyanide RNC (R = t‐Bu, c‐Hx, substituiertes Ph) reagieren mit [Tetra(2,3‐pyrido)‐porphyrazinato]eisen(II) (TPyPFe) zu diaxial substituierten [Tetra(2,3‐pyrido)porphyrazinato]eisen(II)‐Verbindungen TPy‐PFe(RNC)2 1a–8a. Die spektroskopischen und thermischen Eigenschaften der Komplexe werden beschrieben und mit denen der analogen PcFe(CNR)2‐Verbindungen 1b–8b verglichen.
The Ring Opening of Unsymmetrical Allylic, Benzylic, Propargylic, and Si‐Substituted Epoxides by Titanium Acetylides: A Convenient Access to Certain 2‐Substituted 3‐Butyn‐1‐ols
Authors: Krause Norbert , Seebach Dieter
Published: July 2007

Epoxides bearing aryl, alkenyl, alkynyl, and trimethylsilyl substituents react with titanium acetylides at the higher substituted carbon atom exclusively; the 2‐substituted 3‐butyn‐1‐ols thus formed are isolated in 33–79% yield. The dependence of the yield on the solvent, the ratio of the reactands, and their structure is discussed and a reaction mechanism is proposed.
Vinylidene Transition‐metal complexes, VI. The rhodium compounds C5H5Rh(CCHR)PiPr3 as building blocks for the synthesis of heterometallic Di‐ and trinuclear vinylidene‐bridged complexes
Authors: Werner Helmut , Alonso Francesco Javier Garcia , Otto Heiko , Peters Karl , Schnering Hans Georg Von
Published: July 2007

The vinylidene rhodium complex C5H5Rh(  C  CH2)PiPr3 (1) reacts with C6H6Cr(CO)3 upon UV irradiation and with C5H5Mn(CO)2THF at room temperature to give the heterometallic dinuclear compounds [C5H5(PiPr3)Rh(μ‐CCH2)(μ‐CO)Cr(CO)‐C6H6] (4) and [C5H5(PiPr3)Rh(μ‐CCH2(μ‐CO)Mn(CO)C5H5] (6), respectively. Treatment of 6 with HBF4 in ether leads, after metathetical exchange of the anion with NH4PF6, to the PF6 salt of the μ‐ethylidyne cation [C5H5(PiPr3)Rh(μ‐CCH3)(μ‐CO)Mn(CO)C5H5]+ (7). The reactions of 1 and C5H5Rh‐(CCHR)PiPr3 (2: R = Me; 3: R = Ph) with Fe2(CO)9 give the dinuclear complexes [C5H5(PiPr3)Rh(μ‐CCHR)(μ‐CO)Fe(CO)3] (11–13) as the main products. In addition, small amounts of the trinuclear clusters [(μ3‐η1,η2‐CCHR)(μ‐CO)2Fe2Rh(CO)4(PiPr3)C5H5] (14–16) are formed. The protonation of 11–13 with HBF4 gives the ionic compounds [C5H5(PiPr3)Rh(μ‐CCH2R)‐(μ‐CO)Fe(CO)3]BF4 (17–19). The crystal and molecular structures of 6, 11 and 14 have been determined. The two dinuclear complexes 6 and 11 contain unsymmetrical bridging ligands (CO and CCH2) probably as a consequence of the different electronic configuration of the metal atoms. The core of the trinuclear cluster 14 consists of an open RhFeFe triangle which is triply bridged by the CCH2 unit.
Synthese von Tetra(2,3‐naphtho)porphinatoeisen‐ und ‐cobalt‐Komplexen
Authors: Rein Manfred , Hanack Michael
Published: July 2007

2,3‐Naphthalindicarbonsäureanhydrid (8) reagiert mit Essigsäureanhydrid zu 3‐Oxonaphtho[2,3‐c]furan‐1(3H)‐ylidenessigsäure (9), die mit Ammoniak in das Lactam 10 bzw. 11 übergeführt wird. Durch Abspaltung von H2O und CO2 aus 10 entsteht das Benzisoindolderivat 12 (Schema). Durch Umsetzung von 10, 11 oder 12 mit Zinkacetat wird Tetra(2,3‐naphtho)porphinatozink (2,3‐TNPZn) (13) und daraus mit Trifluormethansulfonsäure durch Demetallierung Tetra(2,3‐naphto)porphin (2,3‐TNPH2) erhalten. Aus 2,3‐TNPH2 wird mit Cobalt(II)‐acetat in Pyridin Tetra‐(2,3‐naphtho)porphinatocobalt(II) (2,3‐TNPCo) gewonnen, das mit KCN zum pentakoordinierten 2,3‐TNPCoCN (14), mit SOCl2 zu 2,3‐TNPCoCl (15) reagiert. Tetra(2,3‐naphtho)porphinatoeisen(II) (2,3‐TNPFe) entsteht bei der Reaktion von 1‐[2,3‐Dihydro‐1‐hydroxy‐3‐oxo‐(1H)‐benz[f]isoindol]essigsäure‐Dihydrat (10) mit Eisen(II)‐acetat. Aus 2,3‐TNPFe werden die monomeren, bisaxial substituierten Komplexe 2,3‐TNPFeL2 mit L= py (16), c‐HxNC (17) und dib (18) hergestellt und durch spektroskopische Methoden charakterisiert. Durch Umsetzung von 2,3‐TNPFe mit linearen zweizähnigen Liganden werden die überbrückten Verbindungen [2,3‐TNPFe(L)]n mit L = dib und pyz gewonnen. Infolge des niedrigen Oxidationspotentials des Makrocyclus zeigen alle hier dargestellten Tetra‐(2,3‐naphtho)porhinato‐Verbindungen vergleichsweise hohe Pulverleitfähigkeiten.
Convenient Syntheses of 2‐Nitrophenylsulfen‐(NPS‐)imines by Oxidation of NPS‐Protected Amines and Amino Acid Derivatives
Authors: Heyer Joachim , Dapperheld Steffen , Steckhan Eberhard
Published: July 2007

2‐Nitrophenylsulfenimines 2 of large structural variety are easily available from 2‐nitrophenylsulfenamides 1, by direct and indirect electrochemical oxidation or by using stoichiometric amounts of a triarylamine radical cation salt. In most cases the direct electrochemical method is to be preferred, because of the convenient reaction procedure and the simple workup of the products. Inter‐ and intramolecular addition of nucleophiles to the C  N double bond is possible as shown by two examples.
syn‐[2.2](1,3)Cyclophane durch doppelte Photocyclodimerisierung
Authors: Meier Herbert , Praß Ellen , Noller Klaus
Published: July 2007

Durch doppelte Cyclodimerisierung wird in einer Photolyse in Lösung aus dem 1,3‐disubstituierten Benzol 3 das syn[2.2](1,3)Cyclophan 4 erhalten. Eine kombinierte Belichtung Festkörper/Lösung ergibt bei 5 das analoge System 6 mit Estergruppen. Beide Reaktionen erfolgen streng regiospezifisch durch Kopf‐Kopf‐Verknüpfung und stereospezifisch bezüglich der syn‐Geometrie im Cyclophan und der trans‐Konfiguration der Vierringsubstituenten. Die einzige stereochemische Freiheit besteht in der Anordnung der Vierringe, wobei die Isomeren 4/6a,b,c, den drei möglichen Rotameren in 3 und 5 entsprechen. Während das Gerüst von 4 starr ist, zeigt 6 bei Raumtemp. eine langsame Inversion des zentralen 10‐Rings. Die Aufklärung der Stereoisomeren erfolgt mit NOE‐Messungen.
Notizen N‐Butyl‐N′‐dansylthioharnstoff als fluoreszierender Breitbandkomplexbildner
Authors: König Karl‐Heinz , Boßlet Joachim , Holzner Christoph
Published: July 2007

N‐Butyl‐N′‐dansylthiourea as Fluorescent Broad‐Band Complexing Agent

N‐Butyl‐N′‐dansylthiourea (2) [dansyl = 5‐(dimethylamino)‐1‐naphthylsulfonyl] is obtained by the reaction of dansylamide (1) with butyl isothiocyanate. The compound is a stable, fluorescent complex agent for a broad spectrum of metal ions. The UV spectra and fluorescence of the ligand and some metal complexes are discussed. The fluorescence of the dansyl group is strongly affected by metal ions.
Lichtsensitive Dihydroazulene: Alternativer Syntheseweg – Einfluß von Alkylsubstituenten im Fünfring auf das photochrome Verhalten
Authors: Gierisch Sebastian , Daub Jörg
Published: July 2007

Die Dihydroazulene 1a–d werden ausgehend von Cycloheptatrienylium‐tetrafluoroborat (8) hergestellt. Zwischenverbindungen sind substituierte Cycloheptatriene 10–13. Die Dicyanvinylderivate 12 bzw. 13 werden durch Dehydrogenierung in die Vinylheptafulvene 2 umgewandelt, die wiederum thermisch in 1 umlagern. Dihydroazulene mit Alkylsubstituenten im Fünfring werden auf diesem Weg zugänglich. Außerdem wird die Synthese der auch über die [8 + 2]‐Cycloadditionsroute erhältlichen phenylsubstituierten Dihydroazulene 1a, b beschrieben. Das 3‐Methyl‐2‐phenylderivat 1e konnte neben dem Azulen 15e nur in Spuren nachgewiesen werden. Bei der Untersuchung des photochromen Verhaltens der Verbindungen 1a–d werden signifikante und charakteristische Substituenteneffekte gefunden. Damit wird gezeigt, wie die Schaltzeiten der Photochromie in 1 ⇌ 2 substituenten‐spezifisch verkürzt werden können.
Thermische Cycloadditionen von 1,2‐Dihydropentalen
Authors: Meier Herbert , Pauli Alfred , Molshorn Heinz
Published: July 2007

1,2‐Dihydropentalen (1) ist ein gekreuzt konjugiertes 6π‐Elektronensystem, das in thermischen Cycloadditionen als 2π‐, 4π‐ oder 6π‐Komponente fungieren kann. Es werden die Additionen an Tetraphenylcyclopentadienon (1+2→3), N‐Phenylmaleinimid (1+4→5) und Tropon (1+6→8 bzw. 10) beschrieben. Auf der Basis von MNDO‐Rechnungen werden Peri‐, Regio‐ und Stereoselektivität anhand von primären und sekundären Orbitalwechselwirkungen diskutiert.
Asymmetric Induction in the [2,3] Wittig Rearrangement The Stereoselective Synthesis of Unsaturated Alcohols with Three Contiguous Stereogenic Centers
Authors: Brückner Reinhard
Published: July 2007

The [2,3] Wittig rearrangements of the lithio anions of the allyl propargyl ethers 7 are diastereoselective. A chiral dioxolane in the allyl moiety of 7 controls the configuration of the vinyl group at one of the newly formed stereogenic centers through asymmetric induction. Proper choice of cis‐ or trans‐configurated starting material generates anti (12) or syn (13) 1,3‐dioxygenated systems, respectively, in high selectivity. – It is suggested that the magnitude of the vicinal coupling constant 3JOH,H of the hydroxylic proton can be used to assign the stereochemistry in epimeric syn and anti γ‐alkoxy alcohols.
Synthese mittlerer und großer Ringe, XXIII. Photochemische Umlagerung von 3,6‐Alkanooxepin‐4,5‐dicarbonsäureestern
Authors: Tochtermann Werner , Olsson Gesa , Sczostak Axel , Sönnichsen Frank , Frauenrath Herbert , Runsink Jan , Peters Eva‐Maria , Peters Karl , von Schnering Hans Georg
Published: July 2007

Bestrahlung der 3,6‐Alkanooxepin‐4,5‐dicarbonsäureester 1a–d liefert die tricyclischen Aldehyde 2a–d, deren Konstitutionen durch Röntgenstrukturanalyse von 2a und 2d gesichert wurden. Das analoge disubstituierte 3,6‐Decanooxepin 1e führt unter anderem zum überbrückten Dihydrofuran 4b, für das ebenfalls eine Röntgenstrukturanalyse vorliegt. Mechanistische Untersuchungen zeigen, daß die Photoumlagerung 1 → 2 über Dihydrofurane 3, Cyclopropancarbaldehyde 6 und Cyclopentadiencarbaldehyde 7 verläuft.
Metallkomplexe mit biologisch wichtigen Liganden, IL. Palladium‐ und Platin(II)‐Komplexe von Thioglycinat und Thioalaninat
Authors: Zahn Ingo , Polborn Kurt , Beck Wolfgang
Published: July 2007

Aus Chloro‐phosphan‐Metallverbindungen werden mit Thioglycinat bzw. Thioalaninat die Chelat‐Komplexe (1) (r2 = Et, Ph, n‐Bu) und (2) (M = Pd, Pt) erhalten. Nach den spektroskopischen Daten und der Kristallstrukturbestimmung von 1a (R1 = H; R2 = Et) koordinieren die Anionen der α‐Aminothiosäuren über die Aminogruppe und das S‐Atom. Aus α‐Aminosäure‐chlorid‐Komplexen Cl2Pt(NH2CHRCOCl)2 entstehen mit Thiophenol in heterogener Reaktion die Verbindungen Cl2Pt‐(NH2CHRCOSPh)2 (4) (R = H, CHMe2) mit α‐Aminothiosäure‐S‐phenylester‐Liganden.
(Trifluormethyl)germane, III. Darstellung neuer (Trifluormethyl)germanium‐Chalkogen‐Verbindungen
Authors: Haas Alois , Kutsch H.‐Jürgen , Krüger Carl
Published: July 2007

Durch Halogen‐Chalkogen‐Austauschreaktionen an (CF3)2)GeX2 (X = Cl, I) wurden Bis(trifluormethyl)germachalkogenane [(CF3)2GeE]n (6, 7) E = O, NH, S, Se) von unterschiedlichem Oligomerisierungsgrad erhalten. Die Germoxane [(CF3)2GeO]x und (CF3GeO1,5)x sind im Gegensatz zu den homologen Germathianen und ‐selenanen polymer, wobei die Struktur von [(CF3)2GeO]x (6a) durch eine Kristallstrukturanalyse ermittelt wurde. Durch Umsetzung von CF3GeCl3 mit Triethanolamin wird 1‐(Trifluormethyl)germatran (13) erhalten. Disilaselenan (10) reagiert bei tiefen Temperaturen mit den Chlor (trifluormethyl)‐germanen (CF3)nGeCl4–n monofunktionell unter Erhalt einer SiSe‐Bindung zu (CF3)nGe(SeSiH3)4–n (11) und H3SiCl, von denen die Verbindungen mit n = 3 und 2 isoliert werden konnten. Reaktionen der Iodgermane (CF3)nGeI4–n(1) mit Hg(ECF3)2) (E = S, Se) führen unter Substitution des Iods gegen die ECF3‐Gruppen zur vollständigen Reihe der (Trifluormethyl)(trifluormethylchalkogeno)germane (CF3)nGe(ECF3)4–n (3, 5).
Beiträge zur Chemie des Bors, 196. Darstellung und Reaktionen eines 3‐Amino‐1,2,3‐azaphosphaboriridins
Authors: Kölle Peter , Nöth Heinrich , Paine Robert T.
Published: July 2007

Das 1,2,3‐Azaphosphaboriridin 7, dargestellt durch Enthalogenieren der Boryl(phosphino)amin‐Vorstufe 6, reagiert mit Schwefel und Selen nicht nur unter Ringerweiterung, sondern zugleich unter Oxidation des λ3‐Phosphors zu den neuen Heterocyclen 8. Während sich die aus Cr(CO)6 und W(CO)6 unter Photolyse erzeugten Pentacarbonylfragmente M(CO)5 an das P‐Atom von 7 addieren, erhält man mit MeI kein Phosphoniumsalz. Vielmehr wird das RP‐Fragment von 7 unter Bildung des Iminoborans tmp–tBu als iPr(Me)PI abgespalten.
Mehrfachbindungen zwischen Hauptgruppenelementen und Übergangsmetallen, LIX. Brückenständige Zinn‐Atome in Organomangan‐Komplexen: Aufbau, Strukturchemie und Reaktivität von Mangan–Zinn‐Mehrfachbindungen
Authors: Herrmann Wolfgang A. , Kneuper Heinz‐Josef , Herdtweck Eberhardt
Published: July 2007

Linear und trigonal‐planar konfigurierte Zinn‐Atome aufweisende Organomangan‐Komplexe sind nach zwei Methoden darstellbar: Schrittweise Behandlung des Komplexes (η5‐C5H4CH3)‐Mn(CO)2(THF) (1a) mit Zinn(II)‐chlorid und Zink‐Staub führt ebenso zum Zinn‐Komplex (μ3‐Sn)[(η5‐C5H4CH3)Mn(CO)2]3(2a) wie die Umsetzung von1amit Monostannan, SnH4. Der Pentamethylcyclopentadienyl‐Komplex1bergibt analog die Derivate (μ3‐Sn)[(η5‐C5Me5)(CO)2]3(2b) und (μ‐Sn)[(η5‐C5Me5)Mn‐(CO)2]2(3b). Formal weist der μ3‐Sn‐Komplex2azwei MnSn‐Einfachbindungen und eine MnSn‐Doppelbindung auf (Einkristall‐Röntgenstrukturanalyse).
Synthese, Struktur und Reaktionen von 1,2,3,6‐Tetrahydro‐1,2,3,6‐diphosphadiborin‐Derivaten
Authors: Drieß Matthias , Pritzkow Hans , Siebert Walter
Published: July 2007

Die 1,2,3,6‐Tetrahydro‐1,2,3,6‐diphosphadiborin‐Derivate 3a und 3b entstehen durch Cyclokondensation aus 1,2‐Bis[chlor(dialkylamino)boryl]ethenen 2 und 1,2‐Dikalium‐1,2‐di‐tert‐butyldiphosphandiid. Die Temperaturabhängigkeit der 1H‐NMR‐Spektren von 3b dokumentiert wie bei 2,5‐Dihydro‐1H‐1,2,5‐phosphadiborol‐Derivaten 1 eine erniedrigte Phosphor‐Inversionsbarriere. Die Röntgenstrukturanalyse von 3b zeigt, daß der C2B2P2‐Sechsring im Kristall nicht eben ist und daß die P‐Atome pyramidal koordiniert sind. Versuche zur Substitution der Dialkylaminogruppen an den Boratomen von 3a und 3b mit HCl·Et2O oder tBuLi führen zur Spaltung der BP‐Bindungen. Die Umsetzung von 3a bzw. 3b mit Cr(CO)3(MeCN)3 ergibt keine Tricarbonylchrom‐Komplexe, sondern die Tetracarbonylchrom‐Komplexe 6a bzw. 6b, in denen die Liganden 3a und 3b pentahapto gebunden sind.
Über sterisch gehinderte freie Radikale, XIX. Stabile 4,4′,4″‐trisubstituierte Triphenylmethyl‐Radikale
Authors: Dünnebacke Dieter , Neumann Wilhelm P. , Penenory Alicia , Stewen Ulrich
Published: July 2007

Die Titelradikale (4‐RC6H4)3C· (1), R = F, Cl, Ph, OMe, NO2, tBu, OEt, SMe, CN, CF3, wurden dargestellt, davon die vier letzten erstmalig, und mittels ESR‐Spektroskopie vermessen. aoH, amH und apR werden angegeben. Die ESR‐Signale bleiben im gesamten zugänglichen Temperaturbereich – 30 bis + 100°C in ihrer Intensität unverändert. Daraus folgt, daß alle diese Radikale im genannten Temperaturbereich kinetisch stabil sind, also nicht wie andere Trityle zu Dimerisierungen, etwa α,p‐, α,o‐, α,α‐, neigen.
Photo Diels‐Alder Additions, IV. 1,4‐Photoaddition of α‐(tert‐Butylthio)acrylonitrile to Acylnaphthalenes
Authors: Döpp Dietrich , Memarian Hamid Reza , Krüger Carl , Raabe Eleonore
Published: July 2007

Photoexcited 1‐naphthaldehyde (1a), 1‐acetonaphthone (1b) and 2‐naphthaldehyde (4) add α‐(tert‐butylthio)acrylonitrile (2b) in a [4 + 2] mode with highly regio‐ and stereoselective formation of only one diastereomer of one of the two possible regioisomeric 1,4‐dihydro‐1,4‐ethanonaphthalenes. The configuration of the products is unambiguously derived from an X‐ray crystal structure analysis for adduct 3e and an NOE experiment for compound 5. The only adduct from 1a and 2b could be detected spectroscopically but decomposed upon attempted chromatographic separation of the photolysate. Adducts 3e and 5 show first‐order retro‐cleavage into the starting materials at 50°C in CDCl3 solution with half‐lifes of 4.8 d and 11 h, respectively.
4,4′‐Donor‐substituierte und 6,6′‐difunktionalisierte 2,2′‐Bipyridine
Authors: Neumann Uwe , Vögtle Fritz
Published: July 2007

4,4′‐Donor‐Substituted and 6,6′‐Difunctionalized 2,2′‐Bipyridines

The previously unknown 4,4′‐dimethoxy‐substituted 6,6′‐diacyl‐2,2′‐bipyridines 7, 8 (acyl = acetyl, formyl) are prepared. Some old procedures in the synthetic sequence were optimized.
Komplexchemie perhalogenierter Cyclopentadiene und Alkine, IV. Darstellung, Reaktionen und Strukturen von Alkylthio‐ und Phenylthiosubstituierten (Cyclopentadienyl)mangan‐ und ‐rhodiumkomplexen
Authors: Sünkel Karlheinz , Steiner Doris
Published: July 2007

Die Darstellung und die Kristallstrukturen von (C5Cl4SPh)Rh‐(1,5‐COD)(2b), [C5Cl3(SR)2Mn](CO)3 [R = Ph (4a), Me (4b)] und [C5Cl2(SPh)3]Mn(CO)3 (5a) sowie die Darstellung von [C5Cl5–x (SBu)x]Mn(CO)3 [x = 1 (3b), 2 (4c), 3 (5b)], ferner Reaktionen von [C5Cl2(SR)3]Mn(CO)3 und [C5(SMe)5]Mn(CO)3 mit PdCl(PhCN)2 werden beschrieben. In 2b ist der Cyclopentadienylring nicht planar, und in 5a stehen die drei Phenylringe nahezu parallel.
Tetra‐tert‐butylpentafulvalen als Ligand in Zweikern‐Carbonylkomplexen von Chrom, Molybdän, Wolfram und Eisen
Authors: Jutzi Peter , Schnittger Jörg
Published: July 2007

Reaktion von 1,1′,3,3′‐Tetra‐tert‐butyl‐5,5′‐dihydropentafulvalen (1) mit Mo(CO)6 bzw. mit (CH3CN)3M(CO)3, (M = Cr, W), führt zu den Zweikernkomplexen (η5:η5‐tBu4C10H4)(CO)6M2 (2–4). Umsetzung von 1 mit Fe(CO)5 liefert den Komplex (η5:η5‐tBu4C10H4)(CO)4Fe2 (5). Durch Reaktion äquimolarer Mengen Mo(CO)6, Fe(CO)5 und 1 erhält man neben den Komplexen 3 und 5 die heterodimetallische Verbindung (η5:η5‐tBu4C10H4)(CO)5FeMo (6) mit Molybdän–Eisen‐Bindung.
Cyclophanes, XXVII. [2.2]Indenophane Mono‐ and Dianions: Preparation and Nuclear Magnetic Resonance Spectra
Authors: Frim Ron , Rabinovitz Mordecai , Bodwell Graham , Raulfs Friedrich‐Wilhelm , Hopf Henning
Published: July 2007

The preparation and chemical and physical properties of negatively charged polycyclic cyclophanes are reported. The throughspace electronic interactions and the through‐space anisotropy effects were deduced from proton and carbon nuclear magnetic resonance data. The systems studied belong to two main groups: a) 4nπ‐polycyclic dianions which are paratropic, e.g. [2.2]benzo‐[g]chrysenophane dianion (122−), and b) (4n+ 2)π‐polycyclic mono‐ and dianions, which are diatropic. In the dianions both layers are charged, e. g.syn‐[2.2]indenocyclophane (132−) and itsantiisomer (142−). The monoanions studied are [2.2]benzoindenocyclophane (151−), 4,5,17,18‐tetramethyl[2.2]benzoindenocyclophane (161−), and 12‐methyl[2.2]benzoindenocyclophane (171−). The spectroscopic properties of the layered anions were compared with those of 1,4‐dimethylindenyl anion (111−) and with literature data of neutral cyclophanes, viz.1–11. A differentiation between the anisotropy and charge‐transfer effects has been made and it enables the estimation of the net through‐space interaction.