Hafnium vs. Zirconium, the Perpetual Battle for Supremacy in Catalytic Olefin Polymerization: A Simple Matter of Electrophilicity?
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SUBMITTER: Vittoria A
PROVIDER: S-EPMC8400551 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Pincer-type [Cnaphthyl, Npyridine, Namido]HfMe2 complex is a flagship among the post-metallocene catalysts. In this work, various pincer-type Hf-complexes were prepared for olefin polymerization. Pincer-type [Namido, Npyridine, Namido]HfMe2 complexes were prepared by reacting in situ generated HfMe4 with the corresponding ligand precursors, and the structure of a complex bearing 2,6-Et2C6H3Namido moieties was confirmed by X-ray crystallography. When the ligand precursors of [(CH3)R2Si-C5H3N-C(H)PhN(H)Ar (R = Me or Ph, Ar = 2,6-diisopropylphenyl) were treated with in situ generated HfMe4, pincer-type [Csilylmethyl, Npyridine, Namido]HfMe2 complexes were afforded by formation of Hf-CH2Si bond. Pincer-type [Cnaphthyl, Sthiophene, Namido]HfMe2 complex, where the pyridine moiety in the flagship catalyst was replaced with a thiophene unit, was not generated when the corresponding ligand precursor was treated with HfMe4. Instead, the [Sthiophene, Namido]HfMe3-type complex was obtained with no formation of the Hf-Cnaphthyl bond. A series of pincer-type [Cnaphthyl, Npyridine, Nalkylamido]HfMe2 complexes was prepared where the arylamido moiety in the flagship catalyst was replaced with alkylamido moieties (alkyl = iPr, cyclohexyl, tBu, adamantyl). Structures of the complexes bearing isopropylamido and adamantylamido moieties were confirmed by X-ray crystallography. Most of the complexes cleanly generated the desired ion-pair complexes when treated with an equivalent amount of [(C18H37)2N(H)Me]+[B(C6F5)4]-, which showed negligible activity in olefin polymerization. Some complexes bearing bulky substituents showed moderate activities, even though the desired ion-pair complexes were not cleanly afforded.
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Project description:Catalytic amounts of Co(Sal(tBu,tBu))Cl and organosilane irreversibly isomerize terminal alkenes by one position. The same catalysts effect cycloisomerization of dienes and retrocycloisomerization of strained rings. Strong Lewis bases like amines and imidazoles, and labile functionalities like epoxides, are tolerated.
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Project description:Hafnium complexes have drawn attention for their application as post-metallocene catalysts with unique performance in olefin polymerization. In this work, a series of half-metallocene HfMe2 complexes, bearing a tetrahydroquinoline framework, as well as a series of [Namido,N,Caryl]HfMe2-type post-metallocene complexes, bearing a tetrahydrophenanthroline framework, were prepared; the structures of the prepared Hf complexes were unambiguously confirmed by X-ray crystallography. When the prepared complexes were reacted with anhydrous [(C18H37)2N(H)Me]+[B(C6F5)4]-, desired ion-pair complexes, in which (C18H37)2NMe coordinated to the Hf center, were cleanly afforded. The activated complexes generated from the half-metallocene complexes were inactive for the copolymerization of ethylene/propylene, while those generated from post-metallocene complexes were active. Complex bearing bulky isopropyl substituents (12) exhibited the highest activity. However, the activity was approximately half that of the prototype pyridylamido-Hf Dow catalyst. The comonomer incorporation capability was also inferior to that of the pyridylamido-Hf Dow catalyst. However, 12 performed well in the coordinative chain transfer polymerization performed in the presence of (octyl)2Zn, converting all the fed (octyl)2Zn to (polyolefinyl)2Zn with controlled lengths of the polyolefinyl chain.
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Project description:The polymerization of α-olefins catalyzed by zirconium metallocene catalyst was systematically studied through experiments and density functional theory (DFT) calculations. Having achieved an agreement between theory and experiment, it was found that the effect of the catalyst ligand on the C[double bond, length as m-dash]C insertion reaction was significantly greater than that on the β-H elimination reaction. Therefore, the molecular weight of polymers can be increased by improving the activity of the C[double bond, length as m-dash]C insertion. In addition, in comparison with propylene, the chain length of α-olefins can directly affect the stereotacticity of polymerization products, owing to steric hindrance between the polymer chain and monomer.
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Project description: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.
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Project description:Among transition metal carbides and nitrides, zirconium, and hafnium compounds are the most stable and have the highest melting temperatures. Here we review published data on phases and phase equilibria in Hf-Zr-C-N-O system, from experiment and ab initio computations with focus on rocksalt Zr and Hf carbides and nitrides, their solid solutions and oxygen solubility limits. The systematic experimental studies on phase equilibria and thermodynamics were performed mainly 40-60 years ago, mostly for binary systems of Zr and Hf with C and N. Since then, synthesis of several oxynitrides was reported in the fluorite-derivative type of structures, of orthorhombic and cubic higher nitrides Zr3N4 and Hf3N4. An ever-increasing stream of data is provided by ab initio computations, and one of the testable predictions is that the rocksalt HfC0.75N0.22 phase would have the highest known melting temperature. Experimental data on melting temperatures of hafnium carbonitrides are absent, but minimum in heat capacity and maximum in hardness were reported for Hf(C,N) solid solutions. New methods, such as electrical pulse heating and laser melting, can fill the gaps in experimental data and validate ab initio predictions.
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Project description:Ferroelectricity in crystalline hafnium oxide thin films is strongly investigated for the application in non-volatile memories, sensors and other applications. Especially for back-end-of-line (BEoL) integration the decrease of crystallization temperature is of major importance. However, an alternative method for inducing ferroelectricity in amorphous or semi-crystalline hafnium zirconium oxide films is presented here, using the newly discovered effect of electric field-induced crystallization in hafnium oxide films. When applying this method, an outstanding remanent polarization value of 2P[Formula: see text] = 47 [Formula: see text]C/cm[Formula: see text] is achieved for a 5 nm thin film. Besides the influence of Zr content on the film crystallinity, the reliability of films crystallized with this effect is explored, highlighting the controlled crystallization, excellent endurance and long-term retention.
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Project description:Selective cleavage and subsequent functionalization of C-C single bonds present a fundamental challenge in synthetic organic chemistry. Traditionally, the activation of C-C single bonds has been achieved using stoichiometric transition-metal complexes. Recently, examples of catalytic processes were developed in which use is made of precious metals. However, the use of inexpensive and Earth-abundant group IV metals for catalytic C-C single-bond cleavage is largely underdeveloped. Herein, the zirconium-catalyzed C-C single-bond cleavage and subsequent hydroboration reactions is realized using Cp2ZrCl2 as a catalytic system. A series of structures of various γ-boronated amines are readily obtained, which are otherwise difficult to obtain. Mechanistic studies disclose the formation of a N-ZrIV species, and then a β-carbon elimination route is responsible for C-C single bond activation. Besides zirconium, hafnium exhibits a similar performance for this transformation.
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Project description:The donor strength of bifunctional pyridine-cyclopentadienyl ligands was altered systematically by the introduction of donating groups in the para-position of the pyridine. In the resulting chromium complexes an almost linear correlation between donor strength and the nitrogen-chromium distance as well as the electronic absorption maximum is experimentally observed. The connection of electron-donating groups in the ligand backbone leads to an efficient transfer of the electronic influences to the catalytically active metal centre without restricting it through steric effects. Therefore, catalytic olefin polymerization activity, which is already very high for the previously studied catalysts, increase considerably by attaching para-amino groups to the chelating pyridine or quinoline, respectively. Combining electron-rich indenyl ligands with para-amino substituted pyridines lead to the highest catalytic activities observed so far for this class of organo chromium olefin polymerisation catalysts. The resulting polymers are of ultra-high molecular weight and the ability of the catalysts to incorporate co-monomers is also very high.
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Project description:The pyridylamido hafnium complex (I) discovered at Dow is a flagship catalyst among postmetallocenes, which are used in the polyolefin industry for PO-chain growth from a chain transfer agent, dialkylzinc. In the present work, with the aim to block a possible deactivation process in prototype compound I, the corresponding derivatives were prepared. A series of pyridylamido Hf complexes were prepared by replacing the 2,6-diisopropylphenylamido part in I with various 2,6-R2C6H3N-moieties (R = cycloheptyl, cyclohexyl, cyclopentyl, 3-pentyl, ethyl, or Ph) or by replacing 2-iPrC6H4C(H)- in I with the simple PhC(H)-moiety. The isopropyl substituent in the 2-iPrC6H4C(H)-moiety influences not only the geometry of the structures (revealed by X-ray crystallography), but also catalytic performance. In the complexes bearing the 2-iPrC6H4C(H)-moiety, the chelation framework forms a plane; however, this framework is distorted in the complexes containing the PhC(H)-moiety. The ability to incorporate α-olefin decreased upon replacing 2-iPrC6H4C(H)-with the PhC(H)-moiety. The complexes carrying the 2,6-di(cycloheptyl)phenylamido or 2,6-di(cyclohexyl)phenylamido moiety (replacing the 2,6-diisopropylphenylamido part in I) showed somewhat higher activity with greater longevity than did prototype catalyst I.
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