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.

Isolation of an Elusive Phosphametallacyclobutadiene and Its Role in Reversible Carbon-Carbon Bond Cleavage.

The reactivity of phosphaalkynes, the isolobal and isoelectronic congeners to alkynes, with metal alkylidyne complexes is explored in this work. Treating the tungsten alkylidyne [t BuOCO]W≡Ct Bu(THF)2 (1) with phosphaalkyne (10) results in the formation of [O2 C(t BuC=)W{η2 -(P,C)-P≡C-Ad}(THF)] (13-t BuTHF ) and [O2 C(AdC=)W{η2 -(P,C)-P≡C-t Bu}(THF)] (13-AdTHF ); derived from the formal reductive migratory insertion of the alkylidyne moiety into a W-Carene bond. Analogous to alkyne metathesis, a stable phosphametallacyclobutadiene complex [t BuOCO]W[κ2 -C(t Bu)PC(Ad)] (14) forms upon loss of THF from the coordination sphere of either 13-t BuTHF or 13-AdTHF . Remarkably, the C-C bonds reversibly form/cleave with the addition or removal of THF from the coordination sphere of the formal tungsten(VI) metal center, permitting unprecedented control over the transformation of a tetraanionic pincer to a trianionic pincer and back. Computational analysis offers thermodynamic and electronic reasoning for the reversible equilibrium between 13-t Bu/AdTHF and 14.

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!).

Reactivity Trends of Lewis Acidic Sites in Methylaluminoxane and Some of Its Modifications.

The established model cluster (AlOMe)16(AlMe3)6 for methylaluminoxane (MAO) cocatalyst has been studied by density functional theory, aiming to rationalize the different behaviors of unmodified MAO and TMA-depleted MAO/BHT (TMA = trimethylaluminum; BHT = 2,6-di-tert-butyl-4-methylphenol), highlighted in previous experimental studies. The tendency of the three model Lewis acidic sites A-C to release neutral Al fragments (i.e., AlMe2R; R = Me or bht) or transient aluminum cations (i.e., [AlMeR]+) has been investigated both in the absence and in the presence of neutral N-donors. Sites C are most likely responsible for the activation capabilities of TMA-rich MAO, but TMA depletion destabilizes them, possibly inducing structural rearrangements. The remaining sites A and B, albeit of lower Lewis acidity, should be still able to release cationic Al fragments when TMA-depleted modified MAOs are treated with N-donors (e.g. [AlMe(bht)]+ from MAO/BHT). These findings provide tentative interpretations for earlier observations of donor-dependent ionization tendencies of MAO and MAO/BHT and how TMA depleted MAOs can still be potent activators.

Selective Copper Complex-Catalyzed Hydrodefluorination of Fluoroalkenes and Allyl Fluorides: A Tale of Two Mechanisms.

The transition to more economically friendly small-chain fluorinated groups is leading to a resurgence in the synthesis and reactivity of fluoroalkenes. One versatile method to obtain a variety of commercially relevant hydrofluoroalkenes involves the catalytic hydrodefluorination (HDF) of fluoroalkenes using silanes. In this work it is shown that copper hydride complexes of tertiary phosphorus ligands (L) can be tuned to achieve selective multiple HDF of fluoroalkenes. In one example, HDF of the hexafluoropropene dimer affords a single isomer of heptafluoro-2-methylpentene in which five fluorines have been selectively replaced with hydrogens. DFT computational studies suggest a distinct HDF mechanisms for L2CuH (bidentate or bulky monodentate phosphines) and L3CuH (small cone angle monodentate phosphines) catalysts, allowing for stereocontrol of the HDF of trifluoroethylene.

Organocatalytic C-F Bond Activation with Alanes.

Hydrodefluorination reactions (HDF) of per- and polyfluorinated olefins and arenes by cheap aluminum alkyl hydrides in non-coordinating solvents can be catalyzed by O and N donors. TONs with respect to the organocatalysts of up to 87 have been observed. Depending on substrate and concentration, high selectivities can be achieved. For the prototypical hexafluoropropene, however, low selectivities are observed (E/Z≈2). DFT studies show that the preferred HDF mechanism for this substrate in the presence of donor solvents proceeds from the dimer Me4 Al2 (µ-H)2 ⋅THF by nucleophilic vinylic substitution (SN V)-like transition states with low selectivity and without formation of an intermediate, not via hydrometallation or σ-bond metathesis. In the absence of donor solvents, hydrometallation is preferred but this is associated with inaccessibly high activation barriers at low temperatures. Donor solvents activate the aluminum hydride bond, lower the barrier for HDF significantly, and switch the product preference from Z to E. The exact nature of the donor has only a minimal influence on the selectivity at low concentrations, as the donor is located far away from the active center in the transition states. The mechanism changes at higher donor concentrations and proceeds from Me2 AlH⋅THF via SN V and formation of a stable intermediate, from which elimination is unselective, which results in a loss of selectivity.

How a Thermally Unstable Metal Hydrido Complex Can Yield High Catalytic Activity Even at Elevated Temperatures.

Despite their instability in ethereal solvents, organotitanium hydride catalysts are successfully employed in catalysis at moderate to high temperatures (110 °C), even in the presence of alcohols. It is shown computationally (bond dissociation energy (BDE) analysis and energetic profile for regeneration) and experimentally (EPR studies and kinetic studies), with the specific example of hydrodefluorination (HDF), that despite the long standing belief, regeneration of Ti-H bonds from Ti-F bonds using silanes is endergonic. The resulting low concentration of Ti-H species is crucial for the catalytic stability of those systems. The resting state in the catalysis is a Ti-F species. The most promising silanes for regeneration are not the ones that have the strongest Si-F bond, but the ones that show the largest difference in Si-F and Si-H BDEs.

Structure and Chemistry of SeFx(CN)4-x Compounds.

Several new SeF2(CN)2-donor complexes with N or O based donor molecules are reported. Due to orbital overlap effects 12-crown-4 (1,4,7,10-tetraoxacyclododecane) shows unsymmetric ether oxygen coordination. Solvent coordination (secondary bonding interactions, SBI) in SeFx(CN)4-x compounds is weak and does not influence decomposition pathways (neutral and anionic). Barriers for decomposition are relatively high in SeF2(CN)2 but decrease significantly in compounds with higher cyanide content. In the presence of fluoride ions, facile substitution pathways exist; however, reductive elimination is also favored. In the absence of fluoride ions decomposition barriers are higher, but so are substitution barriers (σ-metathesis). Therefore, successful isolation of Se(CN)4 appears to be significantly hampered. In addition, previously unknown trifluoromethyliminoseleniumdifluoride was cleanly synthesized utilizing the instability of SeF(CN)3 toward reductive FCN elimination (preferred over the thermodynamically favored NCCN elimination) and subsequent FCN incorporation to SeF4 through double F-migration.

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.

Reversible C-C bond formation in group 4 metal complexes: nitrile extrusion via ß-aryl elimination.

Pyridylamides of zirconium and hafnium with [C,N,N]-ligands reversibly insert nitriles into M-CAr bonds leading to an observable equilibrium between the starting [C,N,N]-complexes and newly formed [N,N,N]-complexes with a ketimide moiety in a 7-membered metallacycle. The discovered reversible insertion of nitriles into M-CAr bonds represents an unprecedented example of ß-aryl elimination from a ketimide ligand in early transition metal complexes. Experimental and computational studies suggest thermodynamic and electronic reasons for this reactivity. Weak orbital overlap between the ketimide nitrogen and the metal, and an unfavorable 7-membered metallacycle destabilize the product of insertion into the M-CAr bond, while the pyridylamide moiety acts as a directing group making the reverse process viable. The influence of non-chelate spectator ligands on the metal center and substituents in nitrile on the thermodynamic stability of the [N,N,N]-complexes was also studied. Exploiting ß-carbon elimination in complexes of early transition metals may extend the range of catalysts that are accessible for C-C activation processes in the future.

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.

Cyclic polyacetylene.

Here we demonstrate the synthesis of cyclic polyacetylene (c-PA), or [∞]annulene, via homogeneous tungsten-catalysed polymerization of acetylene. Unique to the cyclic structure and evidence for its topology, the c-PA contains >99% trans double bonds, even when synthesized at -94 °C. High activity with low catalyst loadings allows for the synthesis of temporarily soluble c-PA, thus opening the opportunity to derivatize the polymer in solution. Absolute evidence for the cyclic topology comes from atomic force microscopy images of bottlebrush derivatives generated from soluble c-PA. Now available in its cyclic form, initial characterization studies are presented to elucidate the topological differences compared with traditionally synthesized linear polyacetylene. One advantage to the synthesis of c-PA is the direct synthesis of the trans-transoid isomer. Low defect concentrations, low soliton concentration, and relatively high conjugation lengths are characteristics of c-PA. Efficient catalysis permits the rapid synthesis of lustrous flexible thin films of c-PA, and when doped with I2, they are highly conductive (398 (±76) Ω-1 cm-1).

SPAAC iClick: progress towards a bioorthogonal reaction in-corporating metal ions.

Combining strain-promoted azide-alkyne cycloaddition (SPAAC) and inorganic click (iClick) reactivity provides access to metal 1,2,3-triazolates. Experimental and computational insights demonstrate that iClick reactivity of the tested metal azides (LM-N3, M = Au, W, Re, Ru and Pt) depends on the accessibility of the azide functionality rather than electronic effects imparted by the metal. SPAAC iClick reactivity with cyclooctyne is observed when the azide functionality is sterically unencumbered, e.g. [Au(N3)(PPh3)] (Au-N3), [W(η3-allyl)(N3)(bpy)(CO)2] (W-N3), and [Re(N3)(bpy)(CO)3] [bpy = 2,2'-bipyridine] (Re-N3). Increased steric bulk and/or preequilibria with high activation barriers prevent SPAAC iClick reactivity for the complexes [Ru(N3)(Tp)(PPh3)2] [Tp = tris(pyrazolyl)borate] (Ru-N3), [Pt(N3)(CH3)(PiPr3)2] [iPr = isopropyl] (Pt(II)-N3), and [Pt(N3)(CH3)3]4 ((PtN3)4). Based on these computational insights, the SPAAC iClick reactivity of [Pt(N3)(CH3)3(P(CH3)3)2] (Pt(IV)-N3) was successfully predicted.

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.

Partially fluorinated butatrienes: a coupled cluster study.

The geometries of 19 different partially fluorinated butatrienes and their related butenyne isomers have been calculated at the Møller-Plesset second order perturbation theory level with Dunning's valence triple-zeta basis set. Final energies were determined at the CCSD(T)/cc-pVQZ level of theory. Increasing fluorine substitution has only a limited effect on the bond lengths but a substantial effect on the angles. The CCC bond angles of 4 of the 5 partially fluorinated butatrienes show a deviation of more than 2 degrees from collinearity, therefore representing angle-strained butatrienes. Increasing degree of fluorination has a substantial effect on the isomerization energies. The energy difference between the least stable enyne nonfluorinated at the acetylenic center and the most stable enyne fluorinated at the acetylenic center decreases from 66.8 kJ/mol, in case of the monofluorinated system, to 29.7 kJ/mol in the triple fluorinated system. The acetylenic F substitution is crucial in raising the energies of fluorinated but-1-en-3-yne relative to their butatriene isomers. Within the triple fluorinated system and unprecedented for all discussed molecules, 1,1,4-trifluoro-but-1-en-3-yne represents the only molecule fluorinated at the acetylenic center that is more stable than its triene isomer.

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.

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.

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.