The effect of the amido substituent on polymer molecular weight in propene homopolymerisation by titanium cyclopentadienyl-amide catalysts

In the homopolymerisation of propene by the cyclopentadienyl-amide titanium catalyst systems [η5,η1-C5H4(CH2)2NR]TiCl2/MAO and [η5,η1-C5H4(CH2)2NR]Ti(CH2Ph)2/B(C6F5)3 (R = tBu, iPr, Me), the catalyst with the smallest substituent (Me) on the amido moiety consistently gives the highest polymer molecular weight. This differs from the trend usually observed in related catalysts with tetramethylcyclopentadienyl-amide ancillary ligands, where larger amide substituents result in higher molecular weights. Based on the present information a hypothesis is formulated in which an increased cation-anion interaction for the less sterically hindered catalyst is responsible for disfavouring chain transfer relative to chain growth.

Vanadium (β-(Dimethylamino)ethyl)cyclopentadienyl Complexes with Diphenylacetylene Ligands

Reduction of the V(III) (β-(dimethylamino)ethyl)cyclopentadienyl dichloride complex [η5:η1-C5H4(CH2)2NMe2]VCl2(PMe3) with 1 equiv of Na/Hg yielded the V(II) dimer {[η5:η1-C5H4(CH2)2NMe2]V(µ-Cl)}2 (2). This compound reacted with diphenylacetylene in THF to give the V(II) alkyne adduct [η5:η1-C5H4(CH2)2NMe2]VCl(η2-PhC≡CPh). Further reduction of 2 with Mg in the presence of diphenylacetylene resulted in oxidative coupling of two diphenylacetylene groups to yield the diamagnetic, formally V(V), bent metallacyclopentatriene complex [η5:η1-C5H4(CH2)2NMe2]V(C4Ph4).

Synthesis of heteroatom end-functionalized polyethene with lanthanide and transition-metal catalysts

Incorporation of heteroatom functionalities in the catalytic formation of polyolefin materials can be accomplished either by copolymerization of the olefin with an olefinic substrate that has a heteroatom-containing substituent, or by using a heteroatom-containing chain-transfer agent. In the first case the functionalities introduced are located in side-groups on the polyolefin backbone, in the second case the functionality will cap the polymer on one end of the chain. The latter strategy has been applied recently using chain-transfer agents with reactive X-H bonds (X = Si, B) in conjunction with group 3 and group 4 metal catalysts. We have sought to apply the capacity of lanthanide metallocenes to perform ethene polymerization as well as C-H activation to this chemistry, using heteroatom-containing hydrocarbons with activated C-H bonds as chain-transfer agents, and to compare this with analogous cationic group 4 metallocenes

Extrinsic and intrinsic controls of zooplankton diversity in lakes

Pelagic crustacean zooplankton were collected from 336 Norwegian lakes covering a wide range of latitude, altitude, lake area, mean depth, production (as chlorophyll a), and fish community structure. Mean zooplankton species richness during the ice-free season was generally low at high latitudes and altitudes. Further, lower species richness was recorded in western lakes, possibly reflecting constraints on migration and dispersal. However, despite obvious spatial limitations, geographic boundaries were only weak predictors of mean zooplankton richness. Similarly, lake surface area did not contribute positively to mean richness such as seen in other ecosystem surveys. Rather, intrinsic factors such as primary production and fish community (planktivore) structure were identified by regression analysis as the major predictors of zooplankton diversity, while a positive correlation was observed between species richness and total zooplankton biomass. However, in spite of a large number of variables included in this study, the predictive power of multiple regression models was modest (<50% variance explained), pointing to a major role for within-lake properties, as yet unidentified intrinsic forces, stochasticity, or dispersal as constraints on zooplankton diversity in these lakes