Triptycene as a scaffold in metallocene catalyzed olefin polymerization.

A set of metallocene olefin polymerization catalysts bearing triptycene moieties in either position 4-5 (complexes Ty1-Ty5) or in position 5-6 (complexes Ty6-Ty8) of the basic dimethylsilyl-bridged bis(indenyl) system has been tested in propene polymerization and in ethene/1-hexene copolymerization. Comparison of the results with QSPR (quantitative structure-property relationship) predictions not parametrized for these exotic ligand variations demonstrates that trends can still be identified by extrapolation. Interestingly, Ty7, upon suitable activation, provides a highly isotactic polypropylene with an exceptional amount of 2,1 regio-errors (8%).

Hafnium vs. Zirconium, the Perpetual Battle for Supremacy in Catalytic Olefin Polymerization: A Simple Matter of Electrophilicity?

The performance of -symmetric -hafnocene catalysts for isotactic polypropylene typically deteriorates at increasing temperature much faster than that of their zirconium analogues. Herein, we analyze in detail a set of five Hf/Zr metallocene pairs-including some of the latest generation catalysts-at medium- to high-polymerization temperature. Quantitative structure-activity relationship (QSAR) models for stereoselectivity, the ratio allyl/vinyl chain ends, and 2,1/3,1 misinsertions in the polymer indicate a strong dependence of polymerization performance on electrophilicity of the catalyst, which is a function of the ligand framework and the metal center.

-Zirconocene Catalysts for Isotactic-Selective Propene Polymerization at High Temperature: A Long Story Finds a Happy Ending.

Absolute rigidity is rare in the "soft" world of organometallics. Here we introduce two cyclopenta[]triptycyl -zirconocene catalysts for isotactic-selective propene polymerization, designed by means of an integrated high-throughput experimentation/quantitative structure-activity relationship modeling approach. An ultrarigid ligand precisely wrapped around the Zr center enforces an enzyme-like lock and key fit, effectively hampering undesired reactive events, even at high temperature.

Multisubstituted -symmetric -metallocenes bearing nitrogen heterocycles: influence of substituents on catalytic properties in propylene polymerization at higher temperatures.

In this work we systematically studied the effects of modifications of substituents on the performance of the isospecific zirconocene-based catalyst family, Me2Si(2-Alk-4-(N-carbazolyl)Ind)ZrX2 (X = Cl, Me), wherein the progenitor was shown to be particularly suitable in high-temperature propylene polymerization processes. In order to obtain the required zirconocenes, we developed a novel synthetic pathway to 4-(N-carbazolyl)indenes through Pd-catalyzed cyclizations of 2,2'-dibromobiaryls with 4-aminoindenes, which were synthesized via Buchwald-Hartwig reaction or electrophilic amination of 4-indenyl Grignard reagents with trimethylsilylmethyl azide. By a number of examples, the anion-promoted rac-to-meso isomerization method was shown to work reliably well for preparation of rac-ZrMe2-complexes.

On the limits of tuning comonomer affinity of 'Spaleck-type'ansa-zirconocenes in ethene/1-hexene copolymerization: a high-throughput experimentation/QSAR approach.

For a set of 40 silicon-bridged C-symmetric ansa-zirconocenes, reactivity ratios in ethene/1-hexene copolymerization were experimentally determined by means of an accurate high-throughput experimentation (HTE) approach, and used to develop quantitative structure-activity relationship (QSAR) models for comonomer affinity using chemically meaningful descriptors. These QSAR models rely almost exclusively on steric descriptors, with the single most important descriptor being the 'openness' of the open quadrants. Catalysts with an unobstructed main insertion pathway, i.

An Integrated High Throughput Experimentation/Predictive QSAR Modeling Approach to -Zirconocene Catalysts for Isotactic Polypropylene.

Compared to heterogenous Ziegler-Natta systems (ZNS), -metallocene catalysts for the industrial production of isotactic polypropylene feature a higher cost-to-performance balance. In particular, the -symmetric (indenyl) -zirconocenes disclosed in the 1990s are complex to prepare, less stereo- and/or regioselective than ZNS, and lose performance at practical application temperatures. The golden era of these complexes, though, was before High Throughput Experimentation (HTE) could contribute significantly to their evolution.

Crystal structures of di-μ-bromido-bis{di-bromido-[η-2-(di-methyl-amino)-inden-yl]zirconium(IV)} and di-bromido-bis-[η-2-(di-methyl-amino)-inden-yl]zirconium(IV).

In the title compounds, [ZrBr(CHN)], (I) and [ZrBr(CHN)], (II), the positions of the η-binding 2-di-methyl-amino-indenyl units are fixed by intra-molecular C-H⋯Br inter-actions involving aromatic or di-methyl-amino H atoms. The binuclear mol-ecule of (I) is located on a general position, while the mononuclear mol-ecule of (II) is situated on a twofold rotation axis. Both Zr atoms in (I) are ligated by one cyclo-penta-dienyl (CP) ring and four Br ligands (two bridging, two terminal), while in (II) the Zr atom is ligated by two CP rings and two terminal Br ligands.

Palladium-catalyzed stereocontrolled vinylation of azoles and phenothiazine.

[reaction: see text] Vinylation of various azoles (pyrrole, indole, carbazole, and their derivatives) and phenothiazine with vinyl bromides catalyzed by palladium-phosphine complexes results in the respective N-vinylazoles in 30-99% yields. This reaction with cis- and trans-beta-bromostyrenes is stereospecific giving the respective products with full retention of configuration.