Deposits of clastic carbonate-dominated (calciclastic) sedimentary slope systems in the rock record have been identified mostly as linearly-consistent carbonate apron deposits, even though most ancient clastic carbonate slope deposits fit the submarine fan systems better. Calciclastic submarine fans are consequently rarely described and are poorly understood. Subsequently, very little is known especially in mud-dominated calciclastic submarine fan systems. Presented in this study are a sedimentological core and petrographic characterisation of samples from eleven boreholes from the Lower Carboniferous of Bowland Basin (Northwest England) that reveals a >250 m thick calciturbidite complex deposited in a calciclastic submarine fan setting. Seven facies are recognised from core and thin section characterisation and are grouped into three carbonate turbidite sequences. They include: 1) Calciturbidites, comprising mostly of highto low-density, wavy-laminated bioclast-rich facies; 2) low-density densite mudstones which are characterised by planar laminated and unlaminated muddominated facies; and 3) Calcidebrites which are muddy or hyper-concentrated debrisflow deposits occurring as poorly-sorted, chaotic, mud-supported floatstones. These

Phd by thesis

J. Appl. Cryst.の発刊に際して

Recent developments in isocyanide based multicomponent reactions in applied chemistry

Multicomponent reactions (MCRs) are fundamentally different from two-component reactions in several aspects. Among the MCRs, those with isocyanides have developed into popular organic-chemical reactions in the pharmaceutical industry for the preparation of compound libraries of low-molecular druglike compounds. With a small set of starting materials, very large libraries can be built up within a short time, which can then be used for research on medicinal substances. Due to the intensive research of the last few years, many new backbone types have become accessible. MCRs are also increasingly being employed in the total synthesis of natural products. MCRs and especially MCRs with isocyanides offer many opportunities to attain new reactions and basic structures. However, this requires that the chemist learns the “language” of MCRs, something that this review wishes to stimulate.

Multicomponent Reactions with Isocyanides.

N-Heterocyclic carbenes have become universal ligands in organometallic and inorganic coordination chemistry. They not only bind to any transition metal, be it in low or high oxidation states, but also to main group elements such as beryllium, sulfur, and iodine. Because of their specific coordination chemistry, N-heterocyclic carbenes both stabilize and activate metal centers in quite different key catalytic steps of organic syntheses, for example, C-H activation, C-C, C-H, C-O, and C-N bond formation. There is now ample evidence that in the new generation of organometallic catalysts the established ligand class of organophosphanes will be supplemented and, in part, replaced by N-heterocyclic carbenes. Over the past few years, this chemistry has been the field of vivid scientific competition, and yielded previously unexpected successes in key areas of homogeneous catalysis. From the work in numerous academic laboratories and in industry, a revolutionary turning point in oraganometallic catalysis is emerging.

http://aether.cmi.ua.ac.be/artikels/Artikels%20Gitte/Artikels/Reviews/NHC-%20liganden%20Herrmann.pdf

N-heterocyclic carbenes: a new concept in organometallic catalysis.

As part of studies aimed at delineating the mechanism of the rhodium complex-catalyzed hydroamination of olefins, the model complexes [Rh(PNP)R] (R = CH31a, C6H51b) have been investigated with regard to oxidative addition reactions. The reaction of I2 with 1a leads to both trans- and cis-[Rh(PNP)(CH3)I2] (trans: 2a, cis: 2a′), whereas with 1b only trans-[Rh(PNP)(C6H5)I2] (2b) is obtained. The rhodium(III) complexes [Rh(PNP)(CH3)RI] (3a,b) are formed by the reaction of 1a,b with CH3I. The new organorhodium(III) complexes 2a,b and 3a,b have been characterized by 31P-, 1H-, and 13C-NMR spectrometry, as well as by EI mass spectrometry. The hydrocarbons RCH3 are reductively eliminated in the reaction of [Rh(PNP)(CH3)RI] (3a,b) with TlBF4 in acetone, while the reaction of 3b and TlBF4 in THF/CH3CN leads to the stable rhodium(III) complex [Rh(PNP)(CH3)(C6H5)(CH3CN)]BF4 (5). Complex 5 has been characterized by X-ray crystallography.

Oxidative Addition Reactions of Organorhodium(I) Complexes Containing the Tridentate Ligand 2,6‐Bis(diphenylphosphanylmethyl)pyridine [Rh(PNP)R] (R = CH3, C6H5) with Iodine and Methyl Iodide and Investigation of the Reductive Elimination

Synthesis and characterization of phospha-palladacycles and their catalytic properties in the olefination of chloro- and bromoarenes

VOCl3 reacts with pyrazolylpyridines in the presence of tBuOH to give new six-coordinate vanadium oxoalkoxo complexes. Changing from tBuOH to tBuOOH does not lead to the corresponding tbutylperoxo complexes but to oxidation of Cl-, which finally results in chlorination of the pyrazole fragment of the chelate ligand. These new V(V) complexes catalyze the epoxidation of allylic alcohols and unfunctionalized olefins in the presence of tBuOOH.

Chlorination of a Pyrazole Ligand in Vanadium(V)alkoxo Complexes(1).

Efficient access to a large chemical space based on new scaffolds with defined 3D conformations and highly variable in the side chains is needed to find novel functional materials Four heterocyclic scaffolds based on a four component Ugi reaction of α-amino acids, oxo components, isocyanides and primary or secondary amines suitably functionalized are described A handful of examples are described for each scaffold

Eberhardt Herdtweck

Papers

Oxidative Addition Reactions of Organorhodium(I) Complexes Containing the Tridentate Ligand 2,6‐Bis(diphenylphosphanylmethyl)pyridine [Rh(PNP)R] (R = CH3, C6H5) with Iodine and Methyl Iodide and Investigation of the Reductive Elimination

Synthesis and characterization of phospha-palladacycles and their catalytic properties in the olefination of chloro- and bromoarenes

Chlorination of a Pyrazole Ligand in Vanadium(V)alkoxo Complexes(1).

Various cyclization scaffolds by a truly Ugi 4-CR

Enantioselektive Lewis-Säure-Katalyse in intramolekularen [2+2]-Photocycloadditionen von Cumarinen†