@article{AndersenBogstedDybkaretal.2015,
  author    = {Andersen, Jens Peter and B{\o}gsted, Martin and Dybk{\ae}r, Karen and Mellqvist, Ulf-Henrik and Morgan, Gareth J. and Goldschmidt, Hartmut and Dimopoulos, Meletios A. and Einsele, Hermann and San Miguel, Jes{\´u}s and Palumbo, Antonio and Sonneveld, Pieter and Johnsen, Hans Erik},
  title     = {Global myeloma research clusters, output, and citations: a bibliometric mapping and clustering analysis},
  series = {PLoS ONE},
  volume    = {10},
  journal   = {PLoS ONE},
  number    = {1},
  doi       = {10.1371/journal.pone.0116966},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-144214},
  pages     = {e0116966},
  year      = {2015},
  abstract  = {Background International collaborative research is a mechanism for improving the development of disease-specific therapies and for improving health at the population level. However, limited data are available to assess the trends in research output related to orphan diseases. Methods and Findings We used bibliometric mapping and clustering methods to illustrate the level of fragmentation in myeloma research and the development of collaborative efforts. Publication data from Thomson Reuters Web of Science were retrieved for 2005-2009 and followed until 2013. We created a database of multiple myeloma publications, and we analysed impact and co-authorship density to identify scientific collaborations, developments, and international key players over time. The global annual publication volume for studies on multiple myeloma increased from 1,144 in 2005 to 1,628 in 2009, which represents a 43\% increase. This increase is high compared to the 24\% and 14\% increases observed for lymphoma and leukaemia. The major proportion (> 90\% of publications) was from the US and EU over the study period. The output and impact in terms of citations, identified several successful groups with a large number of intra-cluster collaborations in the US and EU. The US-based myeloma clusters clearly stand out as the most productive and highly cited, and the European Myeloma Network members exhibited a doubling of collaborative publications from 2005 to 2009, still increasing up to 2013. Conclusion and Perspective Multiple myeloma research output has increased substantially in the past decade. The fragmented European myeloma research activities based on national or regional groups are progressing, but they require a broad range of targeted research investments to improve multiple myeloma health care.},
  language  = {en}
}
@article{AndreattaPauli2015,
  author    = {Andreatta, Marta and Pauli, Paul},
  title     = {Appetitive vs. aversive conditioning in humans},
  series = {Frontiers in Behavioral Neuroscience},
  volume    = {9},
  journal   = {Frontiers in Behavioral Neuroscience},
  number    = {128},
  doi       = {10.3389/fnbeh.2015.00128},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-148614},
  year      = {2015},
  abstract  = {In classical conditioning, an initially neutral stimulus (conditioned stimulus, CS) becomes associated with a biologically salient event (unconditioned stimulus, US), which might be pain (aversive conditioning) or food (appetitive conditioning). After a few associations, the CS is able to initiate either defensive or consummatory responses, respectively. Contrary to aversive conditioning, appetitive conditioning is rarely investigated in humans, although its importance for normal and pathological behaviors (e.g., obesity, addiction) is undeniable. The present study intents to translate animal findings on appetitive conditioning to humans using food as an US. Thirty-three participants were investigated between 8 and 10 am without breakfast in order to assure that they felt hungry. During two acquisition phases, one geometrical shape (avCS+) predicted an aversive US (painful electric shock), another shape (appCS+) predicted an appetitive US (chocolate or salty pretzel according to the participants' preference), and a third shape (CS) predicted neither US. In a extinction phase, these three shapes plus a novel shape (NEW) were presented again without US delivery. Valence and arousal ratings as well as startle and skin conductance (SCR) responses were collected as learning indices. We found successful aversive and appetitive conditioning. On the one hand, the avCS+ was rated as more negative and more arousing than the CS and induced startle potentiation and enhanced SCR. On the other hand, the appCS+ was rated more positive than the CS and induced startle attenuation and larger SCR. In summary, we successfully confirmed animal findings in (hungry) humans by demonstrating appetitive learning and normal aversive learning.},
  language  = {en}
}
@article{AndronicShirakashiPickeletal.2015,
  author    = {Andronic, Joseph and Shirakashi, Ryo and Pickel, Simone U. and Westerling, Katherine M. and Klein, Teresa and Holm, Thorge and Sauer, Markus and Sukhorukov, Vladimir L.},
  title     = {Hypotonic Activation of the Myo-Inositol Transporter SLC5A3 in HEK293 Cells Probed by Cell Volumetry, Confocal and Super-Resolution Microscopy},
  series = {PLoS One},
  volume    = {10},
  journal   = {PLoS One},
  number    = {3},
  doi       = {10.1371/journal.pone.0119990},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-126408},
  year      = {2015},
  abstract  = {Swelling-activated pathways for myo-inositol, one of the most abundant organic osmolytes in mammalian cells, have not yet been identified. The present study explores the SLC5A3 protein as a possible transporter of myo-inositol in hyponically swollen HEK293 cells. To address this issue, we examined the relationship between the hypotonicity-induced changes in plasma membrane permeability to myo-inositol Pino [m/s] and expression/localization of SLC5A3. Pino values were determined by cell volumetry over a wide tonicity range (100-275 mOsm) in myo-inositol-substituted solutions. While being negligible under mild hypotonicity (200-275 mOsm), Pino grew rapidly at osmolalities below 200 mOsm to reach a maximum of ∼3 nm/s at 100-125 mOsm, as indicated by fast cell swelling due to myo-inositol influx. The increase in Pino resulted most likely from the hypotonicity-mediated incorporation of cytosolic SLC5A3 into the plasma membrane, as revealed by confocal fluorescence microscopy of cells expressing EGFP-tagged SLC5A3 and super-resolution imaging of immunostained SLC5A3 by direct stochastic optical reconstruction microscopy (dSTORM). dSTORM in hypotonic cells revealed a surface density of membrane-associated SLC5A3 proteins of 200-2000 localizations/μm2. Assuming SLC5A3 to be the major path for myo-inositol, a turnover rate of 80-800 myo-inositol molecules per second for a single transporter protein was estimated from combined volumetric and dSTORM data. Hypotonic stress also caused a significant upregulation of SLC5A3 gene expression as detected by semiquantitative RT-PCR and Western blot analysis. In summary, our data provide first evidence for swelling-mediated activation of SLC5A3 thus suggesting a functional role of this transporter in hypotonic volume regulation of mammalian cells.},
  language  = {en}
}
@phdthesis{AnjanaVaman2015,
  author    = {Anjana Vaman, Vamadevan Sujatha},
  title     = {LASP1, a newly identified melanocytic protein with a possible role in melanin release, but not in melanoma progression},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-116316},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2015},
  abstract  = {LIM and SH3 protein 1 (LASP1) is a nucleocytoplasmic scaffolding protein. LASP1 interacts with various cytoskeletal proteins via its domain structure and is known to participate in physiological processes of cells. In the present study, a detailed investigation of the expression pattern of LASP1 protein in normal skin, melanocytic nevi and melanoma was carried out and the melanocyte-specific function of LASP1 was analyzed. LASP1 protein was identified in stratum basale of skin epidermis and a very high level was detected in nevi, the benign tumor of melanocyte. In the highly proliferative basal cells, an additional distinct nuclear localization of the protein was noted. In different tumor entities, an elevated LASP1 expression and nuclear localization, correlated positively with malignancy and tumor grade. However, LASP1 level was determined to be very low in melanoma and even reduced in metastases. Melanoma is distinguished as the first tumor tested to date - that displayed an absence of elevated LASP1 expression. In addition no significant relation was observed between LASP1 protein expression and clinicopathological parameters in melanoma. The epidermal melanin unit of skin comprises of melanocytes and keratinocytes. Melanocytes are specialized cells that synthesize the photo protective coloring pigment, melanin inside unique organelles called melanosomes. The presence of LASP1 in melanocytes is reported for the first time through this study and the existence was confirmed by immunoblotting analysis in cultured normal human epidermal melanocyte (NHEM) and in melanoma cell lines, along with the immunohistostaining imaging in normal skin and in melanocytic nevi. LASP1 depletion in MaMel2 cells revealed a moderate increase in the intracellular melanin level independently of de novo melanogenesis, pointing to a partial hindrance in melanin release. Immunofluorescence images of NHEM and MaMel2 cells visualized co-localization of LASP1 with dynamin and tyrosinase concomitant with melanosomes at the dendrite tips of the cells. Melanosome isolation experiments by sucrose density gradient centrifugation clearly demonstrated the presence of LASP1 and the melanosome specific markers tyrosinase and TRP1 in late stage melanosomes. The study identified LASP1 and dynamin as novel binding partners in melanocytes and provides first evidence for the existence of LASP1 and dynamin (a protein well-known for its involvement in vesicle formation and budding) in melanosomes. Co-localization of LASP1 and dynamin along the dendrites and at the tips of the melanocytes indicates a potential participation of the two proteins in the membrane vesicle fission at the plasma membrane. In summary, a possible involvement of LASP1 in the actin-dynamin mediated membrane fission and exocytosis of melanin laden melanosome vesicles into the extracellular matrix is suggested.},
  subject      = {Melanom},
  language  = {en}
}
@phdthesis{Ansorg2015,
  author    = {Ansorg, Kay},
  title     = {Development of Accurate Physically Grounded Force Fields for Intermolecular Cation-\$\pi\$ Interactions based on SAPT Energy Decomposition Analysis and Computational Investigation of Covalent Irreversible Vinyl Sulfone-based Protease Inhibitors},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-131084},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2015},
  abstract  = {Part 1 of this work describes the development of accurate physically grounded force fields for intermolecular Cation-π interactions based on SAPT energy decomposition analysis. The presented results demonstrate the benefits of the used DFT-SAPT method to describe non-bonding interactions. First of all, this method is able to reproduce the high level CCSD(T) energy values but using much less computational time. Second it provides the possibility to separate the total intermolecular interaction energy into several physically meaningful contributions. The relative contributions of the dimers investigated can be seen in Fig. 6.16. In Tab. 6.3 the percentage contribution of the attractive energy parts to the stabilization energy is shown. The polarization energy is important for the NH+...C6H6 interaction, whereas it becomes less crucial considering other dimers. The dispersion energy contribution is large in the case of the C6H6...H2O dimers, whereas it is relatively less important for the NH+...C6H6 interaction. The electrostatic energy contributes a large amount of stabilizing energy in all considered dimer interactions. ...},
  subject      = {Kraftfeld},
  language  = {en}
}
@article{AppelScholzMuelleretal.2015,
  author    = {Appel, Mirjam and Scholz, Claus-J{\"u}rgen and M{\"u}ller, Tobias and Dittrich, Marcus and K{\"o}nig, Christian and Bockstaller, Marie and Oguz, Tuba and Khalili, Afshin and Antwi-Adjei, Emmanuel and Schauer, Tamas and Margulies, Carla and Tanimoto, Hiromu and Yarali, Ayse},
  title     = {Genome-Wide Association Analyses Point to Candidate Genes for Electric Shock Avoidance in Drosophila melanogaster},
  series = {PLoS ONE},
  volume    = {10},
  journal   = {PLoS ONE},
  number    = {5},
  doi       = {10.1371/journal.pone.0126986},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-152006},
  pages     = {e0126986},
  year      = {2015},
  abstract  = {Electric shock is a common stimulus for nociception-research and the most widely used reinforcement in aversive associative learning experiments. Yet, nothing is known about the mechanisms it recruits at the periphery. To help fill this gap, we undertook a genome-wide association analysis using 38 inbred Drosophila melanogaster strains, which avoided shock to varying extents. We identified 514 genes whose expression levels and/or sequences covaried with shock avoidance scores. We independently scrutinized 14 of these genes using mutants, validating the effect of 7 of them on shock avoidance. This emphasizes the value of our candidate gene list as a guide for follow-up research. In addition, by integrating our association results with external protein-protein interaction data we obtained a shock avoidance- associated network of 38 genes. Both this network and the original candidate list contained a substantial number of genes that affect mechanosensory bristles, which are hairlike organs distributed across the fly's body. These results may point to a potential role for mechanosensory bristles in shock sensation. Thus, we not only provide a first list of candidate genes for shock avoidance, but also point to an interesting new hypothesis on nociceptive mechanisms.},
  language  = {en}
}
@phdthesis{Appold2015,
  author    = {Appold, Christian},
  title     = {Symbolische BDD-basierte Modellpr{\"u}fung asynchroner nebenl{\"a}ufiger Systeme},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-137029},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2015},
  abstract  = {Today, information and communication systems are ubiquitous and consist very often of several interacting and communicating components. One reason is the widespread use of multi-core processors and the increasing amount of concurrent software for the efficient usage of multi-core processors. Also, the dissemination of distributed emergent technologies like sensor networks or the internet of things is growing. Additionally, a lot of internet protocols are client-server architectures with clients which execute computations in parallel and servers that can handle requests of several clients in parallel. Systems which consist of several interacting and communicating components are often very complex and due to their complexity also prone to errors. Errors in systems can have dramatic consequenses, especially in safety-critical areas where human life can be endangered by incorrect system behavior. Hence, it is inevitable to have methods that ensure the proper functioning of such systems. This thesis aims on improving the verifiability of asynchronous concurrent systems using symbolic model checking based on Binary Decision Diagrams (BDDs). An asynchronous concurrent system is a system that consists of several components, from which only one component can execute a transition at a time. Model checking is a formal verification technique. For a given system description and a set of desired properties, the validity of the properties for the system is decided in model checking automatically by software tools called model checkers. The main problem of model checking is the state-space explosion problem. One approach to reduce this problem is the use of symbolic model checking. There, system states and transitions are not stored explicitely as in explicit model checking. Instead, in symbolic model checking sets of states and sets of transitions are stored and also manipulated together. The data structure which is used in this thesis to store those sets are BDDs. BDD-based symbolic model checking has already been used successful in industry for several times. Nevertheless, BDD-based symbolic model checking still suffers from the state-space explosion problem and further improvements are necessary to improve its applicability. Central operations in BDD-based symbolic model checking are the computation of successor and predecessor states of a given set of states. Those computations are called image computations. They are applied repeatedly in BDD-based symbolic model checking to decide the validity of properties for a given system description. Hence, their efficient execution is crucial for the memory and runtime requirements of a model checker. In an image computation a BDD for a set of transitions and a BDD for a set of states are combined to compute a set of successor or predecessor states. Often, also the size of the BDDs to represent the transition relation is critical for the successful use of model checking. To further improve the applicability of symbolic model checking, we present in this thesis new data structures to store the transition relation of asynchronous concurrent systems. Additionally, we present new image computation algorithms. Both can lead to large runtime and memory reductions for BDD-based symbolic model checking. Asynchronous concurrent systems often contain symmetries. A technique to exploit those symmetries to diminish the state-space explosion problem is symmetry reduction. In this thesis we also present a new efficient algorithm for symmetry reduction in BDD-based symbolic model checking.},
  subject      = {Programmverifikation},
  language  = {de}
}
@article{ArdeltEbbingAdamsetal.2015,
  author    = {Ardelt, Peter U. and Ebbing, Jan and Adams, Fabian and Reiss, Cora and Arap, Wadih and Pasqualini, Renata and Bachmann, Alexander and Wetterauer, Ulrich and Riedmiller, Hubertus and Kneitz, Burkard},
  title     = {An anti-ubiquitin antibody response in transitional cell carcinoma of the urinary bladder},
  series = {PLoS ONE},
  volume    = {10},
  journal   = {PLoS ONE},
  number    = {3},
  doi       = {10.1371/journal.pone.0118646},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-143711},
  pages     = {e0118646},
  year      = {2015},
  abstract  = {Background To use combinatorial epitope mapping ("fingerprinting") of the antibody response to identify targets of the humoral immune response in patients with transitional cell carcinoma (TCC) of the bladder. Methods A combinatorial random peptide library was screened on the circulating pool of immunoglobulins purified from an index patient with a high risk TCC (pTa high grade plus carcinoma in situ) to identify corresponding target antigens. A patient cohort was investigated for antibody titers against ubiquitin. Results We selected, isolated, and validated an immunogenic peptide motif from ubiquitin as a dominant epitope of the humoral response. Patients with TCC had significantly higher antibody titers against ubiquitin than healthy donors (p<0.007), prostate cancer patients (p<0.0007), and all patients without TCC taken together (p<0.0001). Titers from superficial tumors were not significantly different from muscle invasive tumors (p = 0.0929). For antibody response against ubiquitin, sensitivity for detection of TCC was 0.44, specificity 0.96, positive predictive value 0.96 and negative predictive value 0.41. No significant titer changes were observed during the standard BCG induction immunotherapy. Conclusions This is the first report to demonstrate an anti-ubiquitin antibody response in patients with TCC. Although sensitivity of antibody production was low, a high specificity and positive predictive value make ubiquitin an interesting candidate for further diagnostic and possibly immune modulating studies.},
  language  = {en}
}
@phdthesis{ArjonaEsteban2015,
  author    = {Arjona Esteban, Alhama},
  title     = {Merocyanine Dyes as Organic Semiconductors for Vacuum-processed Solar Cell and Transistor Devices},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-129096},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2015},
  abstract  = {The present thesis comprises the synthesis of new functional merocyanine dyes, the study of their electro-optical properties as well as solid state packing and their application as p-type semiconductor materials in transistor and solar cell devices. The absorption properties of the obtained compounds could be modified by variation of the donor unit, the introduction of electron-withdrawing substituents in the acceptor unit or elongation of the polymethine chain. For a particular dye, the absorption band could be shifted by more than 160 nm by increasing the solvent polarity due to a conformational switch between a merocyanine-like and a cyanine-like structure. Single crystal analyses revealed that the studied dyes tend to pack either in an antiparallel fashion forming dimers with no overall dipole moment or in a staircase-like pattern where the dipole moments point to the same direction and are only balanced by another staircase oriented in the opposite direction (stair dimer). With respect to application as semiconductor materials, the latter packing arrangement resulted most favorable for charge carrier mobility. We concluded that this packing motif is preserved in the solar cell devices, where the selenium-containing dye afforded the highest performance of this series for an optimized planar-mixed heterojunction solar cell (6.2 \%).},
  subject      = {Merocyanine},
  language  = {en}
}
@phdthesis{Arnold2015,
  author    = {Arnold, Nicole},
  title     = {Reaktivit{\"a}t von Boranen gegen{\"u}ber {\"U}bergangsmetall-Lewis-Basen},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-125447},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2015},
  abstract  = {Im Rahmen der vorliegenden Arbeit wurden Dihydroborane (H2BR) sowie Dihalogenborane (X2BR) mit {\"U}bergangsmetall-Lewis-Basen umgesetzt und die Reaktivit{\"a}t der auf diese Weise erhaltenen {\"U}bergangsmetall-Bor-Komplexe eingehend untersucht. So wurde eine Serie neuer Borylkomplexe des Typs trans-[Pt{B(Br)R'}Br(PR3)2] dargestellt und mit Salzen schwach-koordinierender Anionen umgesetzt. Diese Studien sollten die Triebkraft f{\"u}r die Bildung kationischer Borylenkomplexe n{\"a}her beleuchten. Die experimentellen Ergebnisse zeigen, dass eine Substitution in ortho-Position des borgebundenen Arylliganden f{\"u}r den notwendigen [1,2]-Halogenshift vom Bor- zum Platinzentrum und somit zur Realisierung einer Pt=B-Mehrfachbindung unabdingbar ist. Demnach reagieren Komplexe mit para-substituierten Arylliganden bei Halogenidabstraktion aus Borylkomplexen zu T-f{\"o}rmigen, kationischen Borylplatinkomplexen, w{\"a}hrend die Duryl-substituierten Analoga unter [1,2]-Halogenwanderung in kationische Borylenplatinkomplexe {\"u}berf{\"u}hrt werden. Neben dem Substitutionsmuster des borgebundenen Arylliganden wurde auch der Einfluss des Phosphanliganden untersucht. Die Molek{\"u}lstrukturen der Borylkomplexe 2 und 4 im Festk{\"o}rper zeigen grundlegende Unterschiede im strukturellen Aufbau. Der Durylsubstituent ist in 2 im Vergleich zur (Ph-4-tBu)-Einheit in 4 deutlich aus der {Br2-Pt-B-Br1}-Ebene herausgedreht (2: Pt-B-C1-C2: 31.4(1); 4: 4.3(7)°), was vermutlich einen [1,2]-Halogenshift in 2 beg{\"u}nstigt. Die Pt-B-Bindungen der kationischen Borylenkomplexe 6 (1.861(5) {\AA}) und 7 (1.863(5) {\AA}) sind deutlich k{\"u}rzer als im neutralen Borylkomplex 2 (2.004(4) {\AA}), was ein eindeutiger Beleg f{\"u}r den Mehrfachbindungscharakter der Pt-B-Bindungen in 6 und 7 ist. Demzufolge scheint der sterische Anspruch des borgebundene Arylsubstituenten entscheidend f{\"u}r den Reaktionspfad bei Halogenidabstraktionen und somit f{\"u}r die Bildung kationischer Borylenplatinkomplexe zu sein, w{\"a}hrend diesen Studien zu Folge der Einfluss der Ligandensph{\"a}re am Platinzentrum eher eine untergeordnete Rolle spielt. Des Weiteren gelang die Synthese der neuartigen heteroleptischen Platinkomplexe [Pt(cAACMe)(PiPr3)] (13) und [Pt(cAACMe)(PCy3)] (14) durch Umsetzung von [Pt(PCy3)2] und [Pt(PiPr3)2] mit dem cyclischen (Alkyl)(Amino)Carben cAACMe (Schema 34, A), bzw. durch Umsetzung von [Pt(nbe)2(PCy3)] (Schema 34, B) mit cAACMe. Die Darstellung des literaturbekannten homoleptischen Komplexes [Pt(cAACMe)2] (11) konnte durch Reaktion von [Pt(nbe)3] mit cAACMe deutlich vereinfacht werden bei gleichzeitiger Steigerung der Ausbeute (96\%, Literatur: 79\%). Die ungew{\"o}hnlich intensiv orangene Farbe dieser Verbindungsklasse geht laut DFT-Rechnungen auf die elektronische Anregung aus dem HOMO in das LUMO zur{\"u}ck, wobei haupts{\"a}chlich die π-Wechselwirkungen zwischen den Platin- und Carbenkohlenstoffatomen des cAACMe-Liganden beteiligt sind (DFT-Rechnungen von Dr. Mehmet Ali Celik). Auch in ihren strukturellen Eigenschaften sind sich 11 - 14 sehr {\"a}hnlich, wohingegen deutliche Unterschiede in deren Elektrochemie und Reaktivit{\"a}t beobachtet wurden. So konnte f{\"u}r 11 eine quasi-reversible Oxidationswelle (E1/2 = -0.30 V gegen [Cp2Fe]/[Cp2Fe]+ in THF) bestimmt werden, w{\"a}hrend die heteroleptischen Komplexe 13 und 14 (Epa = -0.09 V; -0.11 V) sowie deren Vorl{\"a}ufer [Pt(PCy3)2] und [Pt(PiPr3)2] (Epa = 0.00 V; +0.12 V) irreversible Oxidationswellen zeigen. Demnach kann 13 und 14 im Vergleich zu [Pt(PCy3)2] und [Pt(PiPr3)2] ein gr{\"o}ßeres Reduktionsverm{\"o}gen zugeordnet werden. Reaktivit{\"a}tsstudien zeigen, dass der homoleptische Komplex 11 inert gegen{\"u}ber vielen Substraten wie z.B. Boranen, Diboranen(4) und Lewis-S{\"a}uren ist. Im Gegensatz dazu haben sich die heteroleptischen Komplexe 13 und 14 als deutlich reaktiver erwiesen, womit diese eine Mittelstellung zwischen 11 und der Spezies [Pt(PR3)2] einnimmt. Die Umsetzung von [Pt(cAACMe)(PiPr3)] (13) mit BBr3 und Br2BPh lieferte die Borylkomplexe 18 und 19, welche vollst{\"a}ndig charakterisiert wurden. Die Reaktivit{\"a}t von 13 und 14 gegen{\"u}ber den Lewis-S{\"a}uren GaCl3 und HgCl2 zeigt ebenfalls Analogien zu der von Bis(phosphan)platinkomplexen. Reaktion mit GaCl3 f{\"u}hrte hierbei zur Bildung der MOLP-Komplexe [(cAACMe)(PiPr3)Pt→GaCl3] (21) und [(cAACMe)(PCy3)Pt→GaCl3] (22), w{\"a}hrend die oxidative Addition der Hg-Cl-Bindung an das Platinzentrum von 14 im Komplex [PtCl(HgCl)(cAACMe)(PiPr3)] (23) resultierte. Die Synthese von 23 gelang auch durch Umsetzung mit Kalomel unter Abscheidung eines {\"A}quivalentes elementaren Quecksilbers. Ein weiterer Schwerpunkt dieser Arbeit lag auf der {\"U}bergangsmetall-vermittelten Dehydrokupplung von Dihydroboranen. Die Umsetzung von [Pt(cAACMe)(PiPr3)] (13) mit BBr3 und Br2BPh lieferte die Borylkomplexe 18 und 19, welche vollst{\"a}ndig charakterisiert wurden. Die Reaktivit{\"a}t von 13 und 14 gegen{\"u}ber den Lewis-S{\"a}uren GaCl3 und HgCl2 zeigt ebenfalls Analogien zu der von Bis(phosphan)platinkomplexen. Reaktion mit GaCl3 f{\"u}hrte hierbei zur Bildung der MOLP-Komplexe [(cAACMe)(PiPr3)Pt→GaCl3] (21) und [(cAACMe)(PCy3)Pt→GaCl3] (22), w{\"a}hrend die oxidative Addition der Hg-Cl-Bindung an das Platinzentrum von 14 im Komplex [PtCl(HgCl)(cAACMe)(PiPr3)] (23) resultierte. Die Synthese von 23 gelang auch durch Umsetzung mit Kalomel unter Abscheidung eines {\"A}quivalentes elementaren Quecksilbers. Ein weiterer Schwerpunkt dieser Arbeit lag auf der {\"U}bergangsmetall-vermittelten Dehydrokupplung von Dihydroboranen. Vor Beginn dieser Reaktivit{\"a}tsstudien wurde zun{\"a}chst eine vereinfachte Syntheseroute f{\"u}r Dihydroborane entwickelt. Durch Umsetzung von Cl2BDur mit HSiEt3 konnte auf diese Weise der Syntheseaufwand deutlich verringert und die Ausbeute an H2BDur von 74\% auf 98\% deutlich gesteigert werden. Zur Dehydrokupplung wurden neben Gold-, Rhodium- und Iridiumkomplexen auch Platinkomplexe mit H2BDur umgesetzt. Die Untersuchungen mit Gold- und Rhodiumverbindungen erwiesen sich hierbei als erfolglos und die Umsetzung der Iridiumpincerkomplexe [(PCP)IrH2] 26 und 27 (tBuPCP, AdPCP) mit H2BDur lieferte die Boratkomplexe 28 und 29 mit κ2-koordinierten {H2BHDur}-Liganden. Analog konnte bei Umsetzung von 26 mit H2BThx der Boratkomplex 30 spektroskopisch beobachtet, jedoch nicht isoliert werden. Bei den Komplexen 28 - 30 handelt es sich um die ersten κ2-σ:σ-Dihydroboratkomplexe mit sterisch anspruchsvollen Arylsubstituenten. Neben den Iridiumpincerkomplexen wurde auch der Komplex [Cp*IrCl2]2 mit H2BDur umgesetzt. Die Bildung des Boratkomplexes 34 ist mit einem [1,2]-Shift eines Chloratoms von Iridium auf das Borzentrum verbunden. Die Reaktivit{\"a}t von H2BDur gegen{\"u}ber [Pt(PCy3)2] zeigte eine starke Abh{\"a}ngigkeit h{\"a}ngt von der St{\"o}chiometrie. Bei der 1:1-Umsetzung konnten sowohl die farblosen Verbindungen trans-[(PCy3)2PtH2] und Cy3P→BH2Dur (48) isoliert werden, als auch die beiden dunkelroten Verbindungen [(Cy3P)3Pt3(2-B2Dur2)] (36) und [{(PCy3)Pt}4(2-BDur)2(4-BDur)] (37), kristallographisch untersucht werden. Der B-B-Abstand im π-Diborenkomplex 36 (1.614(6) {\AA}) deutet eindeutig auf die Gegenwart einer B=B-Doppelbindung hin, wobei das Diboren side-on gebunden an zwei der drei Platinatome des Pt3-Ger{\"u}sts koordiniert ist. Die Zusammensetzung von 36 und 37 konnte auch durch Elementaranalysen best{\"a}tigt werden. Die Bildung von 36 und 37 deuten auch darauf hin, dass bei dieser Art der Dehydrokupplung multimetallische Wechselwirkungen eine wichtige Rolle f{\"u}r die Stabilisierung der borzentrierten Liganden spielen. So konnten bei der Reaktion von [Pt(PCy3)2] mit zwei {\"A}quivalenten H2BDur neben Cy3P→BH2Dur (48) auch zwei weitere zweikernige Platinverbindungen isoliert und vollst{\"a}ndig charakterisiert werden. Erhitzen der Reaktionsl{\"o}sung auf 68°C f{\"u}r 170 Minuten f{\"u}hrte hierbei zur Bildung von [{(Cy3P)Pt}2(μ-BDur)(ƞ2:(μ-B)-HB(H)Dur)] (38) mit zwei verbr{\"u}ckenden borzentrierten Liganden, einem Borylen- (BDur) und einem Boranliganden (BH2Dur), welche im 11B{1H}-NMR Spektrum bei δ = 101.3 und δ = 32.8 ppm detektiert wurden. Die R{\"o}ntgenstrukturanalyse von 38 l{\"a}sst einen signifikanten σ-BH-Hinbindungsanteil des Boranliganden zu einem der Platinzentren vermuten, was einen anteiligen Pt2→B-Bindungscharakter andeutet. Dieser Befund konnte auch durch DFT-Rechnungen von Dr. William Ewing best{\"a}tigt werden. Die Studien haben auch gezeigt, dass die Bildung von 38 {\"u}ber eine Zwischenstufe verl{\"a}uft, den hypercloso-Cluster [{(Cy3P)HPt}2(μ-H){μ:ƞ2-B2Dur2(μ-H)}] (39) mit einer tetraedrischen {Pt2B2}-Einheit, zwei terminalen Pt-H-Bindungen sowie je einen die Pt-Pt- bzw. B-B-Bindung verbr{\"u}ckenden Hydridliganden. 39 erwies sich als anf{\"a}llig gegen{\"u}ber H2-Eliminierung und lagert bei Raumtemperatur innerhalb von Tagen, bzw. bei 68°C innerhalb einer Stunde unter B-B-Bindungsbruch quantitativ in 38 um, welche selbst keinen direkten Bor-Bor-Kontakt mehr aufweist. Auf Grundlage der beschriebenen Resultate wurde zudem ein einfacher Zugang zu zweikernigen Platinkomplexen entwickelt. Demnach gelang es, den literaturbekannten zweikernigen Komplex [Pt2(μ:ƞ2-dppm)3] (50) (dppm = Ph2PCH2PPh2) durch Umsetzung von [Pt(nbe)3] mit dppm in guten Ausbeuten zu synthetisieren. Des Weiteren wurde die Reaktivit{\"a}t von 50 gegen{\"u}ber verschiedenen Lewis-S{\"a}uren untersucht. Ein Großteil dieser Umsetzungen war mit der Bildung von schwer l{\"o}slichen Feststoffen verbunden, weshalb lediglich bei der Reaktion mit Br2BPh und Br2BMes geringe Mengen an definiertem Produkt isoliert und durch R{\"o}ntgenstrukturanalyse charakterisiert werden konnten. Demnach f{\"u}hrte die Umsetzung von 50 mit Br2BPh oder Br2BMes zur oxidativen Addition beider B-Br-Bindungen an je eines der Platinzentren und der Bildung der verbr{\"u}ckenden Borylenplatinkomplexe 51 und 52. NMR-spektroskopische Studien deuteten eine analoge Reaktivit{\"a}t von Br2BDur und Br2BFc an, wobei die Komplexe 53 und 54 noch nicht vollst{\"a}ndig charakterisiert werden konnten.},
  subject      = {Metallorganische Verbindungen},
  language  = {de}
}