Construction of Bis-pyrazole Based Co(II) Metal-Organic Frameworks and Exploration of Their Chirality and Magnetic Properties

In continuation of our interest in pyrazole based multifunctional metal-organic frameworks (MOFs), we report herein the construction of a series of Co(II) MOFs using a bis-pyrazole ligand and various benzene polycarboxylic acids. Employment of different acids has resulted in different architectures ranging from a two-dimensional grid network, porous nanochannels with interesting double helical features such as supramolecular chicken wire, to three-dimensional diamondoid networks. One of the distinguishing features of the network is their larger dimensions which can be directly linked to a relatively larger size of the ligand molecule. Conformational flexibility of the ligand also plays a decisive role in determining both the dimensionality and topology of the final structure. Furthermore, chirality associated with helical networks and magnetic properties of two MOFs have also been investigated.

Combinatorial Crystal Synthesis: Structural Landscape of Phloroglucinol:1,2-bis(4-pyridyl)ethylene and Phloroglucinol:Phenazine

A large number of crystal forms, polymorphs and pseudopolymorphs, have been isolated in the phloroglucinol-dipyridylethylene (PGL:DPE) and phloroglucinol-phenazine (PGL:PHE) systems. An understanding of the intermolecular interactions and synthon preferences in these binary systems enables one to design a ternary molecular solid that consists of PGL, PHE, and DPE, and also others where DPE is replaced by other heterocycles. Clean isolation of these ternary cocrystals demonstrates synthon amplification during crystallization. These results point to the lesser likelihood of polymorphism in multicomponent crystals compared to single-component crystals. The appearance of several crystal forms during crystallization of a multicomponent system can be viewed as combinatorial crystal synthesis with synthon selection from a solution library. The resulting polymorphs and pseudopolymorphs that are obtained constitute a crystal structure landscape.

Synthesis, antioxidant, and cytotoxic activities of bis(oxazolyl/thiazolyl/imidazolyl)amidomethanesulfonyl Acetamides

A new class of bis(oxazolyl/thiazolyl/imidazolyl)amidomethanesulfonyl acetamides was prepared from the respective (oxazolyl/thiazolyl/imidazolyl)carbamoyl-methylthio acetic acid and studied their antioxidant activity and cytotoxic activitity against A549 lung adenocarcinoma cells. The methyl-substituted sulfonyl bisoxazoles exhibited excellent radical scavenging activity. On the other hand, the chloro-substituted sulfonyl bisthiazoles (IC50 = 49 A mu M) and sulfonyl bisimidazoles (IC50 = 24 A mu M) showed noticeable cytotoxic activity on A549 cells.

Exploring the Crystal Structure Landscape with a Heterosynthon Module: Fluorobenzoic Acid:1,2-Bis(4-pyridyl)ethylene 2:1 Cocrystals

The crystal structure landscape of the 2:1 benzoic acid:dipyridylethylene cocrystal (BA:DPE-I) is explored experimentally with fluoro-substituted benzoic acids and extended with studies employing the Cambridge Structural Database (CSD). The interpretation of the cocrystal landscape is facilitated by considering the kinetically favored and robust acidpyridine heterosynthon as a modular unit. Information based on high-throughput crystallography shows that polymorphs and pseudopolymorphs may belong to the same landscape but arise from different crystallization pathways because of complex and different kinetic features, and secondary synthon preferences. Using the CSD as a guide, the coformer was changed from 1,2-bis(4-pyridyl)ethylene (DPE-I) to 1,2-bis(4-pyridyl)ethane (DPE-II) and this provides an extended interpretation of the BA:DPE-I cocrystal landscape, also highlighting the complexity of the kineticthermodynamic dichotomy during the molecule-to-crystal progression.

Raumordnung in der AWZ: Mittlere Anlandungen der deutschen und internationalen Fischereiflotten aus deutschen Nordseegewässern im Zeitraum von 2000 bis 2004

The pressure of users other than shipping and fishery on the national EEZs for territorial claims has increased in recent years. So it becomes necessary to carry out a spatial planning for which all users have to indicate their recent and planned future activities. For the German waters in the North Sea a first attempt was made to calculate the mean international landings for the commercially important fish and crustacean species on the spatial scale of ICES-rectangles. The relationships between the German and international landings per species are listed in a table and the distribution of the landings for each species within the area are shown in 13 figures.

Fischlarven der westlichen Ostsee – Biodiversitätsuntersuchungen von 2000 bis 2005

Fish larvae surveys provide information on the species composition in an area of investigation and leads to a better understanding of the entire fish community. Since 2000 every year in April/May an ichthyoplankton survey in ICES-Subdivision 22 and 24 has been performed to sample the plankton community in the western Baltic Sea. One objective was to acquire indicators of possible changes in the natural structures of the fish community. The time series derived from the Bongo-Net samples is too short to show a trend in larval densities. Up to now samples in the western Baltic Sea yielded only low mean densities. According to the reproductive biology the fish species were divided in three major groups: -Fish species with a long developmental phase in the plankton community -Small short living species with benthic eggs and a reduced planktonic phase -Guests without local spawning populations Species were identified, which were absent in the plankton of the western Baltic Sea in the 1960s and 1970s.

30. Sitzung des Codex Alimentarius Komitees für Fische und Fischerzeugnisse in Agadir, Marokko, vom 28.9. bis 2.10.2009

The Codex Committee on Fish and Fishery Products held its 30th Session in Agadir, Morocco from 28 September to 2 October 2009, at the kind invitation of the Government of Morocco. The Session was chaired by Dr Bjørn Røthe Knudsen, Regional Director of the Norwegian Food Safety Authority. The Session was attended by 218 delegates representing 78 Member States, one Member Organization (EC) and 1 international organization.

Untersuchungen des Zanderbestandes in den deutschen Küstengewässern der Ostsee von 1992 bis 2002

Pike-perch is an important resource for the coastal fishery in the brackish waters of the eastern part of the coast. For the conservation of the stocks regulation measures (minimum landing size, closed season and minimum mesh size) have been introduced since many years. Basic biological material of the last decade sampled from the commercial fishery and for recruitment by a standard trawl survey. For the “Eastern stock” this paper presents the results concerning age distribution, year-class strengths, growth, proportion spawners, natural mortality and yield-per-recruit analyses.

Fischarten der westlichen Ostsee – Untersuchungen von 2000 bis 2002

Ichthyoplankton provides information on the species com-position in an area of investigation and leads to a better understanding of the entire fish community. Every year since 1993 May/June (from 2000 in April/May) an ichthyoplankton survey in ICES Subdivision 22 and 24 has been done to sample the plankton community in the western Baltic Sea. One objective was to acquire indicators of possible changes in the natural structures of the fish com-munity. The time series derived from the Bongo-Net samples is too short to show a trend in larval densities. Up to now samples in the western Baltic Sea yielded only low mean densities. According to the reproductive biology the fish species were divided in three major groups: •Fish species with a long developmental phase in the plankton community •Small short lived species with benthic eggs and a reduced planktonic phase •Guests without local spawning populations. Species were identified, which were absent in the plankton of the western Baltic Sea in the 1960s and 1970s.

Winterfischerei auf Garnelen. Die Anteile der europäischen Garnelenflotten an den Anlandungen von Crangon crangon im Zeitraum Januar bis März der Jahre 1990 bis 1999

„Winter fishery“ on brown shrimp does not imply a special type of fishery. It merely means the continuation of the standard fishing procedure of parts of the fleet during wintertime, when the majority of the mostly smaller vessels stay in harbour due to generally unfavourable weather conditions for their activity. During 1990 to 1999 mean European wide landings in January and February summedup to 854 tonnes making up to only 4 % of the mean annual landings (21 805 t). While German vessels landed0.7 % (68.7 t) of their mean annual landings during that period, the other countries caught about 7 % of their individual, mean annual landings at the same time. The Netherlands and Denmark contributed highest tonnages of 580and 110 tonnes, respectively, to the total European landings, making up 81 % of them. As about 70 % of brown shrimp may carry eggs in January, the winter fishery took a mean total of about 2.15 x 1012brown shrimp eggs out of the stocks in that period annually. As there is no reliable assessment available concerning the brown shrimp stocks, it is despite of these high losses of eggs not possible to trace a negative effect of the winter fishery in scientific terms. However, precautional catch reductions in winter would be in favour of higher survival rates of eggs, which are the carrying source for the recruitment of brown shrimp stocks and catches in forthcoming summer and autumn seasons according to Dutch investigations.

Die deutsche Fischerei auf den "ozeanischen" Rotbarsch (Sebastes mentella) von 1995 bis 1998

Recently, the German redfish fishery displayed a pronounced seasonal pattern in geographic effort distribution and depth. The second and third quarters were the main season when 80 % of the effort was exerted. During the second quarter, the fleet activities were concentrated in international waters close to the Icelandic Exclusive Economic Zone (EEZ), fishing at depths exceeding 600 m. In contrast, the catches in the third quarter were taken mainly inside the Greenland EEZ at depths around 300 m. From 1995 to 1998, the annual effort ranged from 14 000 to 18 000 trawling hours, without a trend. This effort yielded about 18 000 to 21 000 t (international catch > 100 000 t) annually. Since 1996, the catch rate (CPUE) decreased during the main season. The decrease in CPUE should be interpreted as the first reaction of the stock to increased exploitation. The fish size also varied seasonally and peaked during the second quarter at depths exceeding 600 m. Here, males were bigger than females and both sexes were equally frequent. The increase of fish size with increasing depth did not contribute to the hypothesis of two separate pelagic redfish stocks above and below 500 m. In contrast, the close relation between fish size and depth point to the so-called “deeper-bigger phenomenon” which was found in numerous fish stocks. Very few redfish in the catches were immature.

Die Ostsee-Fischereikommission setzt stärker auf biologische Vorsorge. Ergebnisse der Internationalen Ostsee-Fischereikommission (International Baltic Sea Fishery Commission - IBSFC) vom 7. bis 11. September 1998 in Warschau

Die Tagung setzte den während der vorigen Jahrestagung zu beobachtenden Kurs einer Schwerpunktverlagerung generell fort. Diese ist durch die stärkere Berücksichtigung des Vorsorgeansatzes im Fischereimanagement auf der Grundlage wissenschaftlicher Empfehlungen des ACFM (Management-Komitee für Fischerei) des ICES gekennzeichnet. Damit traten die in der Vergangenheit fischereipolitisch dominierten nationalen Managementinteressen weitestgehend in den Hintergrund und trugen somit zu einer sachlichen Tagungsatmosphäre bei. Wichtigste Tagungsthemen waren die Ausnutzung der nationalen Quoten für 1997 und 1998 (1. Halbjahr), die Festlegung der zulässigen Gesamtfangmengen (TAC) für die internationalen Fischereien 1999, aber auch Strategien zur Nutzung der lebenden Ressourcen der Ostsee unter den Bedingungen des Vorsorgeansatzes im Fischereimanagement. An den Beratungen nahmen Ländervertreter und Experten Estlands, der EU, Lettlands, Polens und der Russischen Föderation sowie Beobachter des ICES (Internationaler Rat für Meeresforschung) und der HELCOM (Helsinki-Kommission) teil.

Synthetic, structural and mechanistic studies of interactions of carbon, nitrogen, and oxygen nucleophiles with bis-pentamethylcyclopentadienyl zirconium and hafnium derivatives

The reactivity of permethylzirconocene and permethylhafnocene complexes with various nucleophiles has been investigated. Permethylzirconocene reacts with sterically hindered ketenes and allenes to afford metallacycle products. Reaction of these cummulenes with permethylzirconocene hydride complexes affords enolate and σ-allyl species, respectively. Reactions which afford enolate products are nonstereospecific, whereas reactions which afford allyl products initially give a cis-σ-allyl complex which rearranges to its trans isomer. The mechanism of these reactions is proposed to occur either by a Lewis Acid-Lewis Base interaction (ketenes) or by formation of a π-olefin intermediate (allenes).

Permethylzirconocene haloacyl complexes react with strong bases such as lithium diisopropylamide or methylene trimethylphosphorane to afford ketene compounds. Depending on the size of the alkyl ketene substituent, the hydrogenation of these compounds affords enolate-hydride products with varying degrees of stereoselectivity. The larger the substituent, the greater is the selectivity for cis hydrogenation products.

The reaction of permethylzirconocene dihydride and permethylhafnocene dihydride with methylene trimethylphosphorane affords methyl-hydride and dimethyl derivatives. Under appropriate conditions, the metallated-ylide complex 1, (η^5-C_5(CH_3)_5)_2 Zr(H)CH_2PMe_2CH_2, is also obtained and has been structurally characterized by X-ray diffraction techniques. Reaction of 1 with CO affords (η^5-C_5(CH_3)_5)_2 Zr(C,O-η^2 -(PMe_3)HC=CO)H which exists in solution as an equilibrium mixture of isomers. In one isomer (2), the η^2-acyl oxygen atom occupies a lateral equatorial coordination position about zirconium, whereas in the other isomer (3), the η-acyl oxygen atom occupies the central equatorial position. The equilibrium kinetics of the 2→3 isomerization have been studied and the structures of both complexes confirmed by X-ray diffraction methods. These studies suggest a mechanism for CO insertion into metal-carbon bonds of the early transition metals.

Permethylhafnocene dihydride and permethylzirconocene hydride complexes react with diazoalkanes to afford η^2-N, N' -hydrazonido species in which the terminal nitrogen atom of the diazoalkane molecule has inserted into a metal-hydride or metal-carbon bond. The structure of one of these compounds, Cp*_2Zr(NMeNCTol_2)OH, has been determined by X-ray diffraction techniques. Under appropriate conditions, the hydrazonido-hydride complexes react with a second equivalent of diazoalkene to afford η' -N-hydrazonido-η^2-N, N' -hydrazonido species.

Bis(thiophenolate)pyridine pincer ligands and trivalent zirconocene complexes relevant to early transition metal polymerization catalysts

Two major topics are covered: the first chapter is focused on the development of post-metallocene complexes for propylene polymerization. The second and third chapters investigate the consequences of diisobutylaluminum hydride (HAlⁱBu₂) additives in zirconocene based polymerization systems.

The synthesis, structure, and solution behavior of early metal complexes with a new tridentate LX₂ type ligand, bis(thiophenolate)pyridine ((SNS) = (2-C₆H₄S)₂-2,6-C₅H₃N) are investigated. SNS complexes of Ti, Zr, and Ta having dialkylamido coligands were synthesized and structurally characterized. The zirconium complex, (SNS)Zr(NMe₂)₂, displays C₂ symmetry in the solid state. Solid-state structures of tantalum complexes (SNS)Ta(NMe₂)₃ and (SNS)TaCl(NEt₂)₂ also display pronounced C₂ twisting of the SNS ligand. 1D and 2D NMR experiments show that (SNS)Ta(NMe₂)₃ is fluxional with rotation about the Ta N(amide) bonds occurring on the NMR timescale. The fluxional behavior of (SNS)TaCl(NEt₂)₂ in solution was also studied by variable temperature ¹H NMR. Observation of separate signals for the diastereotopic protons of the methylene unit of the diethylamide indicates that the complex remains locked on the NMR timescale in one diastereomeric conformation at temperatures below -50 °C.

Reduction of Zr(IV) metallocenium cations with sodium amalgam (NaHg) produces EPR signals assignable to Zr(III) metallocene complexes. Thus, chloro-bridged heterobinuclear ansa-zirconocenium cation [((SBI))Zr(μ-Cl)₂AlMe₂]⁺B(C₆F₅)_4¯ (SBI = rac-dimethylsilylbis(1-indenyl)), gives rise to an EPR signal assignable to the complex (SBI)Zr^III(μ-Cl)₂AlMe₂, while (SBI)Zr^III-Me and (SBI)Zr^III(-H)2AlⁱBu₂ are formed by reduction of [(SBI)Zr(μ-Me)₂AlMe₂]⁺B(C₆F₅)_4¯ and [(SBI)Zr(μ-H)₃(AlⁱBu₂)₂]⁺B(C₆F₅)4¯, respectively. These products are also formed, along with (SBI)Zr^III-ⁱBu and [(SBI)Zr^III]⁺ AlR4¯ when (SBI)ZrMe₂ reacts with HAlⁱBu₂, eliminating isobutane en route to the Zr(III) complex. Studies concerning the interconversion reactions between these and other (SBI)Zr(III) complexes and reaction mechanisms involved in their formation are also reported.

The addition of HAlⁱBu₂ to precatalyst [(SBI)Zr(µ-H)₃(AlⁱBu₂)₂]⁺ significantly slows the polymerization of propylene and changes the kinetics of polymerization from 1st to 2nd order with respect to propylene. This is likely due to competitive inhibition by HAlⁱBu₂. When the same reaction is investigated using [(ⁿBuCp)₂Zr(μ-H)₃(AlⁱBu₂)₂]⁺, hydroalumination between propylene and HAlⁱBu₂ is observed instead of propylene polymerization.

Carbon-carbon bond forming reactions from bis(carbene)-platinum(II) complexes and olefin polymerization and oligomerization using group 4 post-metallocene complexes

A long-standing challenge in transition metal catalysis is selective C–C bond coupling of simple feedstocks, such as carbon monoxide, ethylene or propylene, to yield value-added products. This work describes efforts toward selective C–C bond formation using early- and late-transition metals, which may have important implications for the production of fuels and plastics, as well as many other commodity chemicals.

The industrial Fischer-Tropsch (F-T) process converts synthesis gas (syngas, a mixture of CO + H₂) into a complex mixture of hydrocarbons and oxygenates. Well-defined homogeneous catalysts for F-T may provide greater product selectivity for fuel-range liquid hydrocarbons compared to traditional heterogeneous catalysts. The first part of this work involved the preparation of late-transition metal complexes for use in syngas conversion. We investigated C–C bond forming reactions via carbene coupling using bis(carbene)platinum(II) compounds, which are models for putative metal–carbene intermediates in F-T chemistry. It was found that C–C bond formation could be induced by either (1) chemical reduction of or (2) exogenous phosphine coordination to the platinum(II) starting complexes. These two mild methods afforded different products, constitutional isomers, suggesting that at least two different mechanisms are possible for C–C bond formation from carbene intermediates. These results are encouraging for the development of a multicomponent homogeneous catalysis system for the generation of higher hydrocarbons.

A second avenue of research focused on the design and synthesis of post-metallocene catalysts for olefin polymerization. The polymerization chemistry of a new class of group 4 complexes supported by asymmetric anilide(pyridine)phenolate (NNO) pincer ligands was explored. Unlike typical early transition metal polymerization catalysts, NNO-ligated catalysts produce nearly regiorandom polypropylene, with as many as 30-40 mol % of insertions being 2,1-inserted (versus 1,2-inserted), compared to <1 mol % in most metallocene systems. A survey of model Ti polymerization catalysts suggests that catalyst modification pathways that could affect regioselectivity, such as C–H activation of the anilide ring, cleavage of the amine R-group, or monomer insertion into metal–ligand bonds are unlikely. A parallel investigation of a Ti–amido(pyridine)phenolate polymerization catalyst, which features a five- rather than a six-membered Ti–N chelate ring, but maintained a dianionic NNO motif, revealed that simply maintaining this motif was not enough to produce regioirregular polypropylene; in fact, these experiments seem to indicate that only an intact anilide(pyridine)phenolate ligated-complex will lead to regioirregular polypropylene. As yet, the underlying causes for the unique regioselectivity of anilide(pyridine)phenolate polymerization catalysts remains unknown. Further exploration of NNO-ligated polymerization catalysts could lead to the controlled synthesis of new types of polymer architectures.

Finally, we investigated the reactivity of a known Ti–phenoxy(imine) (Ti-FI) catalyst that has been shown to be very active for ethylene homotrimerization in an effort to upgrade simple feedstocks to liquid hydrocarbon fuels through co-oligomerization of heavy and light olefins. We demonstrated that the Ti-FI catalyst can homo-oligomerize 1-hexene to C₁₂ and C₁₈ alkenes through olefin dimerization and trimerization, respectively. Future work will include kinetic studies to determine monomer selectivity by investigating the relative rates of insertion of light olefins (e.g., ethylene) vs. higher α-olefins, as well as a more detailed mechanistic study of olefin trimerization. Our ultimate goal is to exploit this catalyst in a multi-catalyst system for conversion of simple alkenes into hydrocarbon fuels.