Exploratory and dust-bathing behaviour in laying hens kept in commercial aviaries and furnished cages

The aim of the present thesis was to identify management factors that affect the extent of exploratory behaviour (ground pecking, scratching) as well as quantitative and qualitative as-pects of dust-bathing behaviour in laying hens kept in commercial furnished cages (‘small group housing’) and aviaries. Based on the results, it should be considered which management measures can be recommended for farmers to enhance hen welfare. The feasibility of direct observations of dust-bathing behaviour as well as video observations of exploratory and dust-bathing behaviour was tested in two aviaries. The direct observations were judged to be unfeasible under the conditions encountered. For the analysis of the video recordings, different sampling intervals for instantaneous scan sampling, different extents of observation time, and intra- and inter-observer reliabilities were compared and the most ap-propriate observation scheme selected. Applying the selected scheme (observing the first 16 minutes of every hour distributed over two consecutive light days with a sample interval of two minutes), within the range of environmental conditions found in 22 aviaries, pecking, scratching and dust-bathing behaviour was performed on average 25, 2 and 7 % of the obser-vation time. Hen numbers in the litter were positively associated with stocking density and group size. More scratching was performed with increasing litter height as well as in humid litter. If no litter had been provided, thus substrate consisted of dust and faeces, a reduced proportion of dust-bathing was found. The same method was then used in 16 furnished cage systems. On average 12 % of the total hen number were found on the scratching mats. The hens spent 8 % of the observed time pecking at the mat, 4 % dust-bathing and 0.4 % scratch-ing. Higher proportions were found on the mats and more dust-bathing behaviour occurred, if substrate was provided. Also with increasing light intensity and stocking density more hens were observed on the mats. More pecking and scratching occurred in conditions of higher stocking density, probably due to social facilitation, and of increased mat area per hen. With increasing mat numbers per cage less pecking was observed. Wider mats led to increased dust-bathing behaviour. Finally, 129 dust-baths recorded in 17 aviaries were analysed in detail. On average they lasted 17 minutes, with the tossing phase taking 69 % of this time, including on average 2 vertical wing shakes and 3 scratches with one leg per minute tossing phase. Dust-bath duration de-creased with increasing litter height. Litter type influenced all recorded parameters: dust-bath duration was highest on straw and lowest on fine material and fine material mixed with straw, where on both also the proportion of the tossing phase was lowest. The number of vertical wing shakes during the dust-bath was highest on straw and lowest on fine material mixed with straw as against the frequency of vertical wing shaking that was lowest on straw and highest on fine material. If dust-bathing hens were disturbed twice or more, dust-bathing duration decreased. With increasing light intensity a decreased proportion of the tossing phase as well as a reduced number of vertical wing shakes were recorded. Possibly the light stimulated the hens to dust-bath more often with less tossing behaviour per performance. The observed variation of the dust-bathing parameters could reflect successful adaptation or frustration of the hens. The litter and light conditions on the investigated farms were predominantly restrictive in terms of stimulation of exploration and dust-bathing behaviour. Thus, it was only possible to analyse possible associations between these factors and exploration and dust-bathing behav-iour within the range found. Based on the results the following management recommendations can be given: To allow hens in furnished cages more normal activity, substrate availability should be improved and mat space and light intensity increased. With regard to aviaries as well litter availability should be improved. Litter height should not be too low. Disturbances during dust-bathing should be prevented, but no influencing factors could be identified.

Thermoaktive Bauteilsysteme - Ein neuer simulationstechnischer Berechnungsansatz

Thermoaktive Bauteilsysteme sind Bauteile, die als Teil der Raumumschließungsflächen über ein integriertes Rohrsystem mit einem Heiz- oder Kühlmedium beaufschlagt werden können und so die Beheizung oder Kühlung des Raumes ermöglichen. Die Konstruktionenvielfalt reicht nach diesem Verständnis von Heiz, bzw. Kühldecken über Geschoßtrenndecken mit kern-integrierten Rohren bis hin zu den Fußbodenheizungen. Die darin enthaltenen extrem trägen Systeme werden bewußt eingesetzt, um Energieangebot und Raumenergiebedarf unter dem Aspekt der rationellen Energieanwendung zeitlich zu entkoppeln, z. B. aktive Bauteilkühlung in der Nacht, passive Raumkühlung über das kühle Bauteil am Tage. Gebäude- und Anlagenkonzepte, die träge reagierende thermoaktive Bauteilsysteme vorsehen, setzen im kompetenten und verantwortungsvollen Planungsprozeß den Einsatz moderner Gebäudesimulationswerkzeuge voraus, um fundierte Aussagen über Behaglichkeit und Energiebedarf treffen zu können. Die thermoaktiven Bauteilsysteme werden innerhalb dieser Werkzeuge durch Berechnungskomponenten repräsentiert, die auf mathematisch-physikalischen Modellen basieren und zur Lösung des bauteilimmanenten mehrdimensionalen instationären Wärmeleitungsproblems dienen. Bisher standen hierfür zwei unterschiedliche prinzipielle Vorgehensweisen zur Lösung zur Verfügung, die der physikalischen Modellbildung entstammen und Grenzen bzgl. abbildbarer Geometrie oder Rechengeschwindigkeit setzen. Die vorliegende Arbeit dokumentiert eine neue Herangehensweise, die als experimentelle Modellbildung bezeichnet wird. Über den Weg der Systemidentifikation können aus experimentell ermittelten Datenreihen die Parameter für ein kompaktes Black-Box-Modell bestimmt werden, das das Eingangs-Ausgangsverhalten des zugehörigen beliebig aufgebauten thermoaktiven Bauteils mit hinreichender Genauigkeit widergibt. Die Meßdatenreihen lassen sich über hochgenaue Berechnungen generieren, die auf Grund ihrer Detailtreue für den unmittelbaren Einsatz in der Gebäudesimulation ungeeignet wären. Die Anwendung der Systemidentifikation auf das zweidimensionale Wärmeleitungsproblem und der Nachweis ihrer Eignung wird an Hand von sechs sehr unterschiedlichen Aufbauten thermoaktiver Bauteilsysteme durchgeführt und bestätigt sehr geringe Temperatur- und Energiebilanzfehler. Vergleiche zwischen via Systemidentifikation ermittelten Black-Box-Modellen und physikalischen Modellen für zwei Fußbodenkonstruktionen zeigen, daß erstgenannte auch als Referenz für Genauigkeitsabschätzungen herangezogen werden können. Die Praktikabilität des neuen Modellierungsansatzes wird an Fallstudien demonstriert, die Ganzjahressimulationen unter Bauteil- und Betriebsvariationen an einem exemplarischen Büroraum betreffen. Dazu erfolgt die Integration des Black-Box-Modells in das kommerzielle Gebäude- und Anlagensimulationsprogramm CARNOT. Die akzeptablen Rechenzeiten für ein Einzonen-Gebäudemodell in Verbindung mit den hohen Genauigkeiten bescheinigen die Eignung der neuen Modellierungsweise.

Mechanisms of residue mulch-induced cereal growth increases in West Africa

The use of crop residues (CR) has been widely reported as a means of increasing crop yields across West Africa. However, little has been done to compare the magnitude and mechanisms of CR effects systematically in the different agro-ecological zones of the region. To this end, a series of field trials with millet (Pennisetum glaucum L.), sorghum [Sorghum bicolor (L.) Moench], and maize (Zea mays L.) was conducted over a 4-yr period in the Sahelian, Sudanian, and Guinean zones of West Africa. Soils ranged in pH from 4.1 to 5.4 along a rainfall gradient from 510 to 1300 mm. Treatments in the factorial experiments were three CR rates (0,500, and 2000 kg ha^-1)and several levels of phosphorus and nitrogen. The results showed CR-induced total dry matter (TDM) increases in cereals up to 73% for the Sahel compared with a maximum of 16% in the wetter Sudanian and Guinean zones. Residue effects on weakly buffered Sahelian soils were due to improved P availability and to a protection of seedlings against wind erosion. Additional effects of CR mulching on topsoil properties in the Sahel were a decrease in peak temperatures by 4°C and increased water availability. These mulch effects on soil chemical and physical properties strongly decreased from North to South. Likely explanations for this decrease are the decline of dust deposition and wind erosion hazards, the higher soil clay content, lower air temperature, and a faster decomposition rate of mulch material with increasing rainfall from the Sahel to the Sudanian and Guinean zones.

Soil organic carbon management for sustainable land use in Sudano-Sahelian West Africa

Judged by their negative nutrient balances, low soil cover and low productivity, the predominant agro-pastoral farming systems in the Sudano-Sahelian zone of West Africa are highly unsustainable for crop production intensification. With kaolinite as the main clay type, the cation exchange capacity of the soils in this region, often less than 1 cmol_c kg^-1 soil, depends heavily on the organic carbon (Corg) content. However, due to low carbon sequestration and to the microbe, termite and temperature-induced rapid turnover rates of organic material in the present land-use systems, Corg contents of the topsoil are very low, ranging between 1 and 8 g kg^-1 in most soils. For sustainable food production, the availability of phosphorus (P) and nitrogen (N) has to be increased considerably in combination with an improvement in soil physical properties. Therefore, the adoption of innovative management options that help to stop or even reverse the decline in Corg typically observed after cultivating bush or rangeland is of utmost importance. To maintain food production for a rapidly growing population, targeted applications of mineral fertilisers and the effective recycling of organic amendments as crop residues and manure are essential. Any increase in soil cover has large effects in reducing topsoil erosion by wind and water and favours the accumulation of wind-blown dust high in bases which in turn improves P availability. In the future decision support systems, based on GIS, modelling and simulation should be used to combine (i) available fertiliser response data from on-station and on-farm research, (ii) results on soil productivity restoration with the application of mineral and organic amendments and (iii) our present understanding of the cause-effect relationships governing the prevailing soil degradation processes. This will help to predict the effectiveness of regionally differentiated soil fertility management approaches to maintain or even increase soil Corg levels.

Composition and stability of organic matter fractions in soils under different land use regimes

Soil organic matter (SOM) vitally impacts all soil functions and plays a key role in the global carbon (C) cycle. More than 70% of the terrestric C stocks that participate in the active C cycle are stored in the soil. Therefore, quantitative knowledge of the rates of C incorporation into SOM fractions of different residence time is crucial to understand and predict the sequestration and stabilization of soil organic carbon (SOC). Consequently, there is a need of fractionation procedures that are capable of isolating functionally SOM fractions, i.e. fractions that are defined by their stability. The literature generally refers to three main mechanisms of SOM stabilization: protection of SOM from decomposition by (i) its structural composition, i.e. recalcitrance, (ii) spatial inaccessibility and/or (iii) interaction with soil minerals and metal ions. One of the difficulties in developing fractionation procedures for the isolation of functional SOM fractions is the marked heterogeneity of the soil environment with its various stabilization mechanisms – often several mechanisms operating simultaneously – in soils and soil horizons of different texture and mineralogy. The overall objective of the present thesis was to evaluate present fractionation techniques and to get a better understanding of the factors of SOM sequestration and stabilization. The first part of this study is attended to the structural composition of SOM. Using 13C cross-polarization magic-angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectroscopy, (i) the effect of land use on SOM composition was investigated and (ii) examined whether SOM composition contributes to the different stability of SOM in density and aggregate fractions. The second part of the present work deals with the mineral-associated SOM fraction. The aim was (iii) to evaluate the suitability of chemical fractionation procedures used in the literature for the isolation of stable SOM pools (stepwise hydrolysis, treatments using oxidizing agents like Na2S2O8, H2O2, and NaOCl as well as demineralization of the residue obtained by the NaOCl treatment using HF (NaOCl+HF)) by pool sizes, 13C and 14C data. Further, (iv) the isolated SOM fractions were compared to the inert organic matter (IOM) pool obtained for the investigated soils using the Rothamsted Carbon Model and isotope data in order to see whether the tested chemical fractionation methods produce SOM fractions capable to represent this pool. Besides chemical fractionation, (v) the suitability of thermal oxidation at different temperatures for obtaining stable SOC pools was evaluated. Finally, (vi) the short-term aggregate dynamics and the factors that impact macroaggregate formation and C stabilization were investigated by means of an incubation study using treatments with and without application of 15N labeled maize straw of different degradability (leaves and coarse roots). All treatments were conducted with and without the addition of fungicide. Two study sites with different soil properties and land managements were chosen for these investigations. The first one, located at Rotthalmünster, is a Stagnic Luvisol (silty loam) under different land use regimes. The Ah horizons of a spruce forest and continuous grassland and the Ap and E horizons of two plots with arable crops (continuous maize and wheat cropping) were examined. The soil of the second study site, located at Halle, is a Haplic Phaeozem (loamy sand) where the Ap horizons of two plots with arable crops (continuous maize and rye cropping) were investigated. Both study sites had a C3-/C4-vegetational change on the maize plot for the purpose of tracing the incorporation of the younger, maize-derived C into different SOM fractions and the calculation of apparent C turnover times of these. The Halle site is located near a train station and industrial areas, which caused a contamination with high amounts of fossil C. The investigation of aggregate and density fractions by 13C CPMAS NMR spectroscopy revealed that density fractionation isolated SOM fractions of different composition. The consumption of a considerable part (10–20%) of the easily available O-alkyl-C and the selective preservation of the more recalcitrant alkyl-C when passing from litter to the different particulate organic matter (POM) fractions suggest that density fractionation was able to isolate SOM fractions with different degrees of decomposition. The spectra of the aggregate fractions resembled those of the mineral-associated SOM fraction obtained by density fractionation and no considerable differences were observed between aggregate size classes. Comparison of plant litter, density and aggregate size fractions from soil under different land use showed that the type of land use markedly influenced the composition of SOM. While SOM of the acid forest soil was characterized by a large content (> 50%) of POM, which contained high amounts of spruce-litter derived alkyl-C, the organic matter in the biologically more active grassland and arable soils was dominated by mineral-associated SOM (> 95%). This SOM fraction comprised greater proportions of aryl- and carbonyl-C and is considered to contain a higher amount of microbially-derived organic substances. Land use can alter both, structure and stability of SOM fractions. All applied chemical treatments induced considerable SOC losses (> 70–95% of mineral-associated SOM) in the investigated soils. The proportion of residual C after chemical fractionation was largest in the arable Ap and E horizons and increased with decreasing C content in the initial SOC after stepwise hydrolysis as well as after the oxidative treatments with H2O2 and Na2S2O8. This can be expected for a functional stable pool of SOM, because it is assumed that the more easily available part of SOC is consumed first if C inputs decrease. All chemical treatments led to a preferential loss of the younger, maize-derived SOC, but this was most pronounced after the treatments with Na2S2O8 and H2O2. After all chemical fractionations, the mean 14C ages of SOC were higher than in the mineral-associated SOM fraction for both study sites and increased in the order: NaOCl < NaOCl+HF ≤ stepwise hydrolysis << H2O2 ≈ Na2S2O8. The results suggest that all treatments were capable of isolating a more stable SOM fraction, but the treatments with H2O2 and Na2S2O8 were the most efficient ones. However, none of the chemical fractionation methods was able to fit the IOM pool calculated using the Rothamsted Carbon Model and isotope data. In the evaluation of thermal oxidation for obtaining stable C fractions, SOC losses increased with temperature from 24–48% (200°C) to 100% (500°C). In the Halle maize Ap horizon, losses of the young, maize-derived C were considerably higher than losses of the older C3-derived C, leading to an increase in the apparent C turnover time from 220 years in mineral-associated SOC to 1158 years after thermal oxidation at 300°C. Most likely, the preferential loss of maize-derived C in the Halle soil was caused by the presence of the high amounts of fossil C mentioned above, which make up a relatively large thermally stable C3-C pool in this soil. This agrees with lower overall SOC losses for the Halle Ap horizon compared to the Rotthalmünster Ap horizon. In the Rotthalmünster soil only slightly more maize-derived than C3-derived SOC was removed by thermal oxidation. Apparent C turnover times increased slightly from 58 years in mineral-associated SOC to 77 years after thermal oxidation at 300°C in the Rotthalmünster Ap and from 151 to 247 years in the Rotthalmünster E horizon. This led to the conclusion that thermal oxidation of SOM was not capable of isolating SOM fractions of considerably higher stability. The incubation experiment showed that macroaggregates develop rapidly after the addition of easily available plant residues. Within the first four weeks of incubation, the maximum aggregation was reached in all treatments without addition of fungicide. The formation of water-stable macroaggregates was related to the size of the microbial biomass pool and its activity. Furthermore, fungi were found to be crucial for the development of soil macroaggregates as the formation of water-stable macroaggregates was significantly delayed in the fungicide treated soils. The C concentration in the obtained aggregate fractions decreased with decreasing aggregate size class, which is in line with the aggregate hierarchy postulated by several authors for soils with SOM as the major binding agent. Macroaggregation involved incorporation of large amounts maize-derived organic matter, but macroaggregates did not play the most important role in the stabilization of maize-derived SOM, because of their relatively low amount (less than 10% of the soil mass). Furthermore, the maize-derived organic matter was quickly incorporated into all aggregate size classes. The microaggregate fraction stored the largest quantities of maize-derived C and N – up to 70% of the residual maize-C and -N were stored in this fraction.

Synthese und Charakterisierung neuer symmetrischer und unsymmetrischer Spiro-p-oligophenyle

In der vorliegenden Arbeit wurden neue symmetrische Spiro-p-oligophenyle der allgemeinen Form Spiro-o-Φ[n,n] mit der Gesamtkettenlänge o=2n+2 Phenylringen (o > 10) und der Zahl n der Phenylringe in den p-Oligophenylsubstituenten am Spirobifluorenkern, dargestellt. Neben den symmetrischen Verbindungen wurden erstmals auch unsymmetrische Spiro-p-oligophenyle der allgemeinen Form Spiro-o-Φ[n,m] mit o=n+m+2 (o = 3-7) und n ≠ m synthetisiert. Aufgrund der sehr geringen Löslichkeit der größeren Verbindungen wurden löslichkeitssteigernde Substituenten an den endständigen Phenylringen angebracht. Bei den Verbindungen, die mit Trimethylsilyl-Gruppen (TMS-) in den endständigen meta-Positionen „3“ und „5“ substituiert wurden, konnte die Löslichkeit um mehrere Größenordnungen gesteigert werden, sodass die Darstellung der symmetrischen Verbindungen bis zu einer Kettenlänge von 16 Phenylringen möglich wurde. Nach erfolgreicher Synthese und Aufreinigung wurden die TMS-Gruppen wieder entfernt und die erhaltenen, unsubstituierten Verbindungen charakterisiert. Zusätzlich wurden auch die TMS-Derivate untersucht. Zur Charakterisierung zählten neben der Reinheits- und Strukturanalytik unter anderem auch spektroskopische (UV/Vis-Absorption, Fluoreszenz, Fluoreszenzquantenausbeute), elektrochemische (Cyclovoltammetrie) und thermische (Thermogravimetrie, Dynamische Differenzkalorimetrie) Untersuchungen. Hier wurde unter anderem der Einfluss der Kettenlänge und der Position der Spiroverknüpfung auf isomere Verbindungen gleicher Kettenlänge untersucht. Bei den spektroskopischen Messungen konnte eine Konvergenz der längstwelligen Absorptionsbanden, bzw. kürzestwelligen Fluoreszenzbanden mit zunehmender Kettenlänge beobachtet werden. Die effektive Konjugationslänge konnte so aus experimentellen Daten bestimmt werden zu 12 Phenylringen in der Absorption und 14 Phenylringen in der Fluoreszenz. Bei den Isomeren gleicher Kettenlänge zeigte sich in der Absorption eine hypsochrome Verschiebung der Absorptionsmaxima mit zunehmender Verschiebung der Spiroverknüpfung zum Kettenende hin, während die Position der Spiroverknüpfung keinen messbaren Einfluss auf die Verschiebung der Fluoreszenzbanden hatte. Die Substitution mit TMS in den meta-Positionen zeigte keinen messbaren Einfluss auf die Absorptions- bzw. Fluoreszenzbanden. Die elektrochemischen Untersuchungen zeigten mit zunehmender Kettenlänge eine erleichterte Oxidation und Reduktion, während bei Isomeren gleicher Kettenlänge die Oxidation mit Verschiebung der Spiroverknüpfung zum Kettenende hin erschwert und die Reduktion erleichtert war. Die thermogravimetrischen Analysen (TGA) zeigten eine außerordentlich hohe thermische Stabilität (5% Massenabnahme unter Schutzgas) der Spiro-p-oligophenyle von Td,5% = 474°C bei Spiro-5Φ[1,2] bis 570°C bei Spiro 8Φ[3,3]. Ebenso blieben hohe Rückstandsmassen unter Schutzgas bei 850°C zurück, wie das Beispiel Spiro 8Φ[3,3] mit 68% zeigt. Die Verbindungen zeigten hohe Schmelzpunkte (max. 496°C bei Spiro-6Φ[0,4]) und Glasübergangstemperaturen (max. 434°C bei p-TMS-Spiro-8Φ[3,3]). Viele der Verbindungen, besonders die in den meta-Positionen TMS-substituierten Verbindungen, bildeten stabile amorphe Gläser.

Ferrocene-Based Pyridylphosphine Ligands – Coordination Chemistry of Group 10, 11 and 12 Metals

English: The present thesis describes the synthesis of 1,1’-ferrocendiyl-based pyridylphosphine ligands, the exploration of their fundamental coordination chemistry and preliminary experiments with selected complexes aimed at potential applications. One main aspect is the synthesis of the bidentate ferrocene-based pyridylphosphine ligands 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene, 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene and 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. A specific feature of these ligands is the ball-bearing like flexibility of the ferrocenebased backbone. An additional flexibility element is the rotation around the C–C single bonds. Consequently, the donor atoms can realise a wide range of positions with respect to each other and are therefore able to adapt to the coordination requirements of different metal centres. The flexibility of the ligand also plays a role in another key aspect of this work, which concerns the coordination mode, i. e. bridging vs. chelating. In addition to the flexibility, also the position of the donor atoms to each other is important. This is largely affected by the position of the pyridyl nitrogen (pyrid-2-yl vs. pyrid-3-yl) and the methylen group in 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. Another interesting point is the combination of a soft phosphorus donor atom with a harder nitrogen donor atom, according to the HSAB principle. This combination generates a unique binding profile, since the pi-acceptor character of the P site is able to stabilise a metal centre in a low oxidation state, while the nitrogen sigma-donor ability can make the metal more susceptible to oxidative addition reactions. A P,N-donor combination can afford hemilabile binding profiles, which would be ideal for catalysis. Beyond 1,2-substituted ferrocene derivatives, which are quite successful in catalytic applications, 1,1’-derivatives are rather underrepresented. While a low-yield synthetic pathway to 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene was already described in the literature [I. R. Butler, Organometallics 1992, 11, 74.], it was possible to find a new, improved and simplified synthetic pathway. Both other ligands were unknown prior to this work. Satisfactory results in the synthesis of 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene could be achieved by working in analogy to the new synthetic procedure for 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene. The synthesis of 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene has been handled by the group of Prof. Petr Stepnicka from Charles University, Prague, Czech Republic. The synthesis of tridentate ligands with an analogous heterodentate arrangement, was investigated briefly as a sideline of this study. The major part of this thesis deals with the fundamental coordination chemistry towards transition metals of the groups 10, 11 and 12. Due to the well-established catalytic properties of analogous palladium complexes, the coordination chemistry towards palladium (group 10) is of particular interest. The metals zinc and cadmium (group 12) are also of substantial importance because they are redox-inert in their divalent state. This is relevant in view of electrochemical investigations concerning the utilisation of the ligands as molecular redox sensors. Also mercury and the monovalent metals silver and gold (group 11) are included because of their rich coordination chemistry. It is essential to answer questions concerning aspects of the ligands’ coordination mode bearing in mind the HSAB principle.

Die Carbonylierung acyclischer Diaminocarbene

Das Dissertationsprojekt befasst sich mit dem synthetischen Potential acyclischer Diaminocarbene (aDACs; Verbindungen des Typs (R2N)2C:) und prüft dabei insbesondere deren Reaktivität gegenüber Kohlenmonoxid (CO). Grundlage des Vorhabens ist eine Aufsehen erregende Beobachtung von SIEMELING et al. (Chem. Sci., 2010, 1, 697): Der Prototyp der aDACs, das Bis(diisopropylamino)carben, ist in der Lage CO zu aktivieren. Dabei wird zunächst ein intermediäres Keten des Typs (R2N)2C=C=O generiert, das in Folge einer intramolekularen Reaktion ein stabiles β-Lactamderivat ausbildet. Eine Sensation, schließlich ging man in der Fachwelt bis dato davon aus, dass cyclische und acyclische Diaminocarbene für derartige Reaktionen nicht elektrophil genug seien. Ziel der vorliegenden Arbeit war eine systematische Auslotung der aDAC-Reaktivität gegenüber CO. Im Rahmen der durchgeführten Untersuchungen ist es gelungen, das Feld der literaturbekannten aDACs von 12 auf 19 zu erweitern. Die Carbene, ihre Formamidiniumsalz-Vorstufen, sowie die korrespondierenden Carben–Metallkomplexe konnten in den meisten Fällen vollständig charakterisiert werden. Es konnte gezeigt werden, dass manche Isopropyl-substituierten aDACs in inertem Lösemittel einer β-Umlagerung unterliegen sowie, dass eine solche intramolekulare Reaktivität innerhalb dieser Substanzklasse nicht trivial ist: Zum Teil ganz ähnlich substituierte aDACs sind in Lösung unbegrenzt haltbar. Die Reaktivität gegenüber CO konnte an etwa einem Dutzend aDACs studiert werden. Lediglich in einem Fall zeigte sich das Carben inert. In einem sterisch überfrachteten Fall entstand in einer regio- und stereoselektiven Folgereaktion ein biologisch aktives bicyclisches β-Lactamderivat. In den meisten Fällen ergaben sich betainische Oxyallylspezies des Typs [(R2N)2C]2CO als intermolekulare Folgeprodukte. Die mechanistische Scheidelinie zwischen intra- und intermolekularer Keten-Folgereaktion konnte anhand der Carbonylierung sterisch ganz ähnlich substituierter aDACs aufgezeigt werden. Die gewonnenen Erkenntnisse liefern deutliche Hinweise darauf, dass das chemische Verhalten der aDACs gegenüber CO eher durch feinste elektronische Unterschiede als durch den sterischen Anspruch der Carben-Substituenten beeinflusst wird. Mit Hilfe von In-Situ-IR-Spektroskopie gelang es in manchen Fällen, bei denen eine Isolierung der Carbonylierungsprodukte nicht glückte, die Generierung hochreaktiver Oxyallylspezies zu belegen. Weiterhin konnte im Zuge der In-Situ-IR-Studien das zuvor nur postulierte Diaminoketen als primäres Carbonylierungsprodukt dingfest gemacht werden (ν(C=C=O) = 2085 1/cm): Es handelt sich hierbei um den ersten experimentellen Nachweis eines Diaminoketens überhaupt.