Octahedral Zirconium Salan Catalysts for Olefin Polymerization: Substituent and Solvent Effects on Structure and Dynamics.

Group 4 metal-Salan olefin polymerization catalysts typically have relatively low activity, being slowed down by a pre-equilibrium favoring a non-polymerization active resting state identified as a mer-mer isomer (MM); formation of the polymerization active fac-fac species (FF) requires isomerization. We now show that the chemistry is more subtle than previously realized. Salan variations bearing large, flat substituents can achieve very high activity, and we ascribe this to the stabilization of the FF isomer, which becomes lower in energy than MM. Detailed in situ NMR studies of a fast (o-anthracenyl) and a slow (o-tBu) Salan precursors, suitably activated, indicate that preferred isomers in solution are different: the fast catalyst prefers FF while the slow catalyst prefers a highly distorted MM geometry. Crystal structures of the activated o-anthracenyl substituted complex with a moderately (chlorobenzene) and, more importantly, a weakly coordinating solvent (toluene) in the first coordination sphere emphasize that the active FF isomer is preferred, at least for the benzyl species. Site epimerization (SE) barriers for the fast catalyst (ΔS > 0, dissociative) and the slow catalyst (ΔS < 0, associative) in toluene corroborate the solvent role. Diagnostic NMe 13C chemical shift differences allow unambiguous detection of FF or MM geometries for seven activated catalysts in different solvents, highlighting the role of solvent coordination strength and bulkiness of the ortho-substituent on the isomer equilibrium. For the first time, active polymeryl species of Zr-Salan catalysts were speciated. The slow catalyst is effectively trapped in the inactive MM state, as previously suggested. Direct observation of fast catalysts is hampered by their high reactivity, but the product of the first 1-hexene insertion maintains its FF geometry.

A High-Throughput Approach to Repurposing Olefin Polymerization Catalysts for Polymer Upcycling.

Efficient and economical plastic waste upcycling relies on the development of catalysts capable of polymer degradation. A systematic high-throughput screening of twenty-eight polymerization catalyst precursors, belonging to the catalyst families of metallocenes, ansa-metallocenes, and hemi- and post-metallocenes, in cis-1,4-polybutadiene (PB) degradation reveals, for the first time, important structure-activity correlations. The upcycling conditions involve activation of the catalysts (at 0.18 % catalyst loading) with tri-iso-butyl aluminum at 50 °C in toluene. The data indicate the ability to degrade PB is a general reactivity profile of neutral group 4 metal hydrides. A simple quantitative-structure activity relationship (QSAR) model utilizing two descriptors for the distribution of steric bulk in the active pocket and one measuring the metal ion electrophilicity reveals the degradation ability improves with increased but not overbearing steric congestion and lower electrophilicity.

ansa-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[a]triptycyl ansa-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. Stereodefective units are hardly detectable by 13C NMR in the polymer produced at 120 °C; this corresponds to an enantioselectivity exceeding 6-7 kcal/mol: i.e., less than 1 propene misinsertion every 4000 (and at room temperature, one every ∼40000!).

Of Poisons and Antidotes in Polypropylene Catalysis.

Quenched-flow studies of MgCl2 -supported Ziegler-Natta catalysts were combined for the first time with (13) C NMR fingerprinting of the nascent polymer and conclusively proved that, depending on the catalyst formulation, propene polymerization can be slowed down significantly by the occurrence of the few regiodefects (2,1 monomer insertions), changing active sites into dormant sites. Catalysts modified with ethylbenzoate show little dormancy. The more industrially relevant phthalate based catalysts, instead, are highly dormant and require the presence of H2 to counteract the deleterious effect of this self-poisoning on productivity and stereoselectivity.

Cocatalyst effects in Hf-catalysed olefin polymerization: taking well-defined Al-alkyl borate salts into account.

Hafnium catalysts for olefin polymerization are often very sensitive to the nature of cocatalysts, especially if they contain "free" aluminium trialkyls. Herein, cocatalyst effects in Hf-catalysed propene polymerization are examined for four Hf catalysts belonging to the family of CS-symmetric (Hf-CS-Met) and C2-symmetric (Hf-C2-Met) metallocenes, as well as of octahedral (Hf-OOOO) and pentacoordinated (Hf-PyAm) "post-metallocenes". The performance of the recently developed {[iBu2(PhNMe2)Al]2(µ-H)}+[B(C6F5)4]- (AlHAl) cocatalyst is compared with that of established systems like methylalumoxane, phenol-modified methylalumoxane and trityl borate/tri-iso-butylaluminium. The worst catalytic performance is observed with MAO. Conversely, the best cocatalyst varies depending on the Hf catalyst used and the performance indicator of interest, highlighting the complexity and importance of selecting the right precatalyst/cocatalyst combination. AlHAl proved to be a suitable system for all catalysts tested and, in some cases, it provides the best performance in terms of productivity (e.g. with hafnocenes). Furthermore, it generally leads to high molecular weight polymers, also with catalysts enabling easy chain transfer to Al like Hf-PyAm. This suggests that AlHAl has a low tendency to form heterodinuclear adducts with the cationic active species, therefore preventing the formation of dormant sites and/or termination events by chain transfer to Al.

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%). The previously developed QSPR type models successfully predicted the low regioselectivity of this catalyst, despite the fact that the catalyst structure differs significantly from the benchmark set.

A Hydrocarbon Soluble, Molecular and "Complete" Al-Cocatalyst for High Temperature Olefin Polymerization.

The dinuclear aluminum salt {[iBu2(DMA)Al]2(µ-H)}+[B(C6F5)4]- (AlHAl; DMA = N,N-dimethylaniline) is the prototype of a new class of molecular cocatalysts for catalytic olefin polymerization, its modular nature offering easy avenues for tailoring the activator to specific needs. We report here, as proof of concept, a first variant (s-AlHAl) bearing p-hexadecyl-N,N-dimethylaniline (DMAC16) units, which enhances solubility in aliphatic hydrocarbons. The novel s-AlHAl was used successfully as an activator/scavenger in ethylene/1-hexene copolymerization in a high-temperature solution process.

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

The performance of C2-symmetric ansa-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. Based on this insight, the stronger performance decline of hafnocenes is ascribed to electrophilicity-dependent stabilization effects.

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

Compared to heterogenous Ziegler-Natta systems (ZNS), ansa-metallocene catalysts for the industrial production of isotactic polypropylene feature a higher cost-to-performance balance. In particular, the C2-symmetric bis(indenyl) ansa-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. Herein, we illustrate a Quantitative Structure - Activity Relationship (QSAR) model trained on a robust and highly accurate HTE database. The clear-box QSAR model utilizes, in particular, a limited number of chemically intuitive 3D geometric descriptors that screen various regions of space in and around the catalytic pocket in a modular way thus enabling to quantify individual substituent contributions. The main focus of the paper is on the methodology, which should be of rather broad applicability in molecular organometallic catalysis. Then again, it is worth emphasizing that the specific application reported here led us to identify in a comparatively short time novel zirconocene catalysts rivaling or even outperforming all previous homologues which strongly indicates that the metallocene story is not over yet.

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 C2-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.e. without substituents affecting the open quadrant, show a remarkable insensitivity to further substituent effects, be it in 2-, 4-, 5-, 6- or 7-position or the bridge. We attribute this insensitivity to a shift in rate-limiting step for the comonomer incorporation, from insertion to olefin capture, with the latter being much less sensitive to modulation of the active pocket than the former. This indicates that our best incorporators are already close to the upper limit for comonomer affinity within this catalyst class.

C1-Symmetric Si-bridged (2-indenyl)(1-indenyl) ansa-metallocenes as efficient ethene/1-hexene copolymerization catalysts.

In the search for more efficient single-center ethene/α-olefin copolymerization catalysts, metallocenes bearing a 2-indenyl substituent pattern have largely been ignored in the past. Here, we show that such a structural motif yields competent linear low-density polyethylene (LLDPE) catalysts. They are also relatively easy to synthesize, allowing for a wide structural amplification. A screening of 28 catalysts reveals that the lead catalyst in this study displays high comonomer affinity and molecular weight capability at industrially relevant temperatures. QSAR models show that steric factors likely contribute stronger than electronic factors to the observed substituent trends, both for comonomer affinity and MW capability.

Assignment of Regioirregular Sequences in the 13C NMR Spectrum of Syndiotactic Polypropylene.

The 13C NMR microstructure of a polypropylene (PP) sample is a fundamental source of information on its properties, and also a 'fingerprint' of the catalytic species used to produce it. Likely due to a much greater technological importance, isotactic polymers (i-PP) have been more thoroughly investigated that syndiotactic ones (s-PP). In this paper, we report the first full assignment of regioirregular sequences in s-PP samples made with two well-known molecular catalysts, namely a Cs-symmetric (cyclopentadienyl)(fluorenyl) ansa-zirconocene and a fluxional bis(phenoxyimine)Ti species. The results shed more light on the mechanism of chain propagation at the two catalysts, and open the door to the investigation of more elusive cases like the formation of s-PP blocks in the presence of multi-sited heterogeneous Ziegler-Natta systems.