A DFT Quantum‐Chemical Study of the Structure of Precursors and Active Sites of Catalyst Based on 2,6‐Bis(imino)pyridyl Fe(II) Complexes

Summary: A DFT method has been applied for quantum‐chemical calculations of the molecular structure of charge‐neutral complex LFeMe(μMe)₂AlMe₂ which is formed in system LFeMe₂ + AlMe₃ (L = 2,6‐bis(imino)pyridyl). Calculations suggested the formation of highly polarized complex LFeMe(μMe)₂AlMe₂ ( II ) in system LFeMe₂ + AlMe₃, characterized by r(Fe μMe) = 3.70 Å and r(Al μMe) = 2.08 Å and deficient electron density on fragment [LFeMe]^Q (Q = +0.80 e). Polarization of the complex progresses with the bounding of two AlMe₃ molecules (complex LFeMe(μMe)₂AlMe₂ · 2AlMe₃ ( III )) and with replacement of AlMe₃ by MeAlCl₂ (complex LFeMe(μMe)₂AlCl₂ ( IV )). The activation energy of ethylene insertion into the Fe Me bond of these complexes has been calculated. It was found that the heat of π‐complex formation increases with increasing of polarization extent in the order II < III < IV . Activation energy of the insertion of coordinated ethylene into Fe Me bond decreases in the same order: II > III > IV .

Calculated model complex (NH₃)₃FeMe₂; tridentate bis(imino)pyridyl ligand was substituted by three coplanar NH₃ groups.     

New Kinetic Model of Ethene Polymerization with Cp2ZrCl2 /MAO Catalyst

The kinetics of ethene polymerization catalyzed by Cp₂ZrCl₂ /MAO is studied. A detailed look is taken at the different kinetic models used to describe the polymerization process. Also, a new model was developed on the basis of previous work. The new model takes both the active‐sites mechanism and the reactivation effect of MAO into account. Better agreement between the experimental data and the fitting profile was achieved by applying the new model, when compared with the results from older models. A plausible mechanism of polymerization is outlined.     

A Ditopic Ion‐Pair Receptor Based on Stacked Nucleobase Quartets

Pass the salt, please! State‐of‐the‐art computations indicate that the stacking complex of a guanine quartet and an adenine quartet (G₄A₄) can function as a potent ditopic receptor for NaCl in aqueous solution (see picture; Na⁺, Cl^? yellow, O red, N blue, C black, H white).

     

A kinetic study of metallocene‐catalyzed ethylene polymerization using different aluminoxane cocatalysts

The kinetics of ethylene polymerization using homogeneous Cp₂ZrCl₂/aluminoxane catalysts in toluene has been investigated at 70 °C with an ethylene pressure of 30 psi. Four aluminoxanes were used: methylaluminoxane, modified methylaluminoxanes with a fraction of methyl groups substituted with isobutyl (MMAO‐4) or octyl (MMAO‐12) groups, and polymethylaluminoxane (PMAO‐IP). The cocatalyst‐to‐catalyst ratio, [Al]/[Zr], varied from 1000 to 10,000. The experimental results obtained using the four cocatalysts were compared and a model was proposed to fit the rate of polymerization as a function of polymerization time and [Al]/[Zr] ratio. Molecular weight distributions with polydispersities between three and four indicate the presence of more than one active site type. We proposed a model that explained these broad molecular weight distributions using an unstable active complex that is formed in the early stages of the reaction and is transformed over time to a more stable active complex via an intermediate. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1677–1690, 2007     

Ion‐Pair SN2 Substitution: Activation Strain Analyses of Counter‐Ion and Solvent Effects

The ion‐pair S_N2 reactions of model systems M_nF^n?1+CH₃Cl (M⁺=Li⁺, Na⁺, K⁺, and MgCl⁺; n=0, 1) have been quantum chemically explored by using DFT at the OLYP/6‐31++G(d,p) level. The purpose of this study is threefold: 1) to elucidate how the counterion M⁺ modifies ion‐pair S_N2 reactivity relative to the parent reaction F^?+CH₃Cl; 2) to determine how this influences stereochemical competition between the backside and frontside attacks; and 3) to examine the effect of solvation on these ion‐pair S_N2 pathways. Trends in reactivity are analyzed and explained by using the activation strain model (ASM) of chemical reactivity. The ASM has been extended to treat reactivity in solution. These findings contribute to a more rational design of tailor‐made substitution reactions.     

Experimental and theoretical investigations of the structure of methylaluminoxane (MAO) cocatalysts for olefin polymerization

The structure of methylaluminoxane (MAO), used as a cocatalyst for olefin polymerization, has been investigated by Raman and in situ IR spectroscopy, polymerization experiments, and density functional calculations. From experimental results, a number of quantum chemical calculations, and bonding properties of related compounds, we have suggested a few Me₁₈Al₁₂O₉ cage structures, including a highly regular one with C_3h symmetry, which may serve as models for methylaluminoxane solutions. The cages themselves are rigid but may contain up to three bridging methyl groups on the cage surfaces that are labile and reactive. Bridging methyls were substituted with Cl atoms to form a compound otherwise similar to MAO. Chlorinated MAO is unable to activate a metallocene catalyst, even in the presence of trimethylaluminum (TMA), but allows subsequent activation by regular MAO. With bis(pentamethylcyclopentadienyl)zirconium dichloride, MAO and TMA seem to influence chain termination independently. Several findings previously poorly explained are rationalized with the new model, including the observed lack of reaction products with excess TMA. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3106–3127, 2000     

Fluorine Interactions in a Post‐Metallocene Titanium Catalyst: An ab initio Study

The stability of weak fluorine bonds in homogeneous catalyst is studied at the ab initio level for an arylpyridine post‐metallocene complex. The Ti···F···H_β interaction scheme, involving the agostic bond with titanium and the H‐bond with an H_β in the growing chain, is found to be the the most stable one. A possible optimal overlap involving the fluorine lone pairs is proposed. This three‐center interaction could play a role in the inhibition of H_β transfer to the metal or to the monomer in the termination reactions.

     

Selective separation of strontium by multitopic ion‐pair receptor: A DFT exploration

Selective extraction of a radionuclide in the presence of other interfering ions is one of the vital steps in the back‐end‐of‐the‐nuclear fuel cycle. The presence of interfering cations (such as Ca²⁺) in the radioactive waste and involvement of multiple separation steps are known to be bottlenecks in the efficient Sr²⁺ extraction. Here, using free energy corrected density functional theory, we have proposed a two‐step Sr²⁺ extraction methodology in nitrate media in the presence of interfering Ca²⁺ ion using a multitopic ion‐pair receptor, which was earlier reported to be strongly selective for K⁺ (Kim et al. J. Am. Chem. Soc. 2012, 134 , 1782–1792). To depict the correct free energy trend in the proposed extraction processes, the most probable binding mode of the metal (Sr²⁺, Ca²⁺, and K⁺) nitrates in the host are identified. In excellent agreement with the previously reported experiment, Crown/Pyrrole (C/P) binding is noted to be the most preferable mode for KNO₃, where K⁺ and occupied the Crown (C) and Pyrrole (P) site, respectively. However, the divalent metal ions (Ca²⁺ and Sr²⁺) are noted to marginally prefer Crown/Crown‐Pyrrole (C/CP) mode, in which metal reside at the C site while two nitrates occupy the P site and also simultaneously bind at the outer sphere of C site to coordinate with the metal via monodentate motif. Based on the free energy of extraction, we predict that the selective separation of chemically alike Ca²⁺/Sr²⁺ pair is indeed achievable using this receptor. We propose that once [Sr(NO₃)₂] is extracted in organic media, the receptor's high affinity toward K⁺ in nitrate media can be used to back strip Sr²⁺ to the aqueous phase.     

Polyethylene Made with Combinations of Single‐Site‐Type Catalysts: Monte Carlo Simulation of Long‐Chain Branch Formation

The formation of long‐chain branches (LCBs) during ethylene polymerization with a combination of catalysts was studied by Monte Carlo simulation. The model describes polymerization with a non‐branching catalyst that produces linear macromonomers, and a branching catalyst that produces linear and branched macromonomers. The LCBs are formed when the branching catalyst incorporates a macromonomer. The discussion is based on the three types of chain topology obtained during the synthesis: linear, comb‐branched, or hyperbranched. Simulation results show how the chain length distribution and the number of LCBs change according to the ratio between the two catalysts present in the reactor. The ratio hyperbranched/comb‐branched is defined to evaluate the system composition and the contribution of each catalyst.     

Copolymerization of propylene with higher α‐olefins in the presence of the syndiospecific catalyst i‐Pr(Cp)(9‐Flu)ZrCl2/MAO

The catalyst system i‐Pr(Cp)(9‐Flu)ZrCl₂/methylaluminoxane was used for the synthesis of random syndiotactic copolymers of propylene with 1‐hexene, 1‐dodecene, and 1‐octadecene as comonomers. An investigation of the microstructure by ¹³C NMR spectroscopy revealed that the stereoregularity of the copolymers decreased because of an increase in skipped insertions in the presence of the higher 1‐olefin. The melting temperature of the copolymers, as measured by differential scanning calorimetry (DSC), decreased linearly with increasing comonomer content independently of the comonomer nature. During the DSC heating cycle, an exothermic peak indicating a crystallization process was observed. The decrease in the crystallization temperature with higher 1‐olefin content, measured by crystallization analysis fractionation, indicated a small but significant dependence on the nature of the comonomer. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 128–140, 2002     

Beyond the Halogen Bond: Examining the Limits of Extended Polybromide Networks through Quantum‐Chemical Investigations

The bonding environments of some polybromide monoanions and networks were examined by quantum‐chemical methods to investigate electronic interactions between dibromine–dibromine contacts. Examination of thermodynamic parameters and a bond critical point analysis give strong evidence for such bonding modes, which have been previously treated disparately in the literature. The thermodynamic stability of large polybromides up to [Br₃₇]^? was also predicted by these methods.     

Quantum‐Chemical Study of the FeNCN Conversion‐Reaction Mechanism in Lithium‐ and Sodium‐Ion Batteries

We report a computational study on 3d transition‐metal (Cr, Mn, Fe, and Co) carbodiimides in Li‐ and Na‐ion batteries. The obtained cell voltages semi‐quantitatively fit the experiments, highlighting the practicality of PBE+U as an approach for modeling the conversion‐reaction mechanism of the FeNCN archetype with lithium and sodium. Also, the calculated voltage profiles agree satisfactorily with experiment both for full (Li‐ion battery) and partial (Na‐ion battery) discharge, even though experimental atomistic knowledge is missing up to now. Moreover, we rationalize the structural preference of intermediate ternaries and their characteristic lowering in the voltage profile using chemical‐bonding and Mulliken‐charge analysis. The formation of such ternary intermediates for the lithiation of FeNCN and the contribution of at least one ternary intermediate is also confirmed experimentally. This theoretical approach, aided by experimental findings, supports the atomistic exploration of electrode materials governed by conversion reactions.     

Ion‐Pair SN2 Reaction of OH− and CH3Cl: Activation Strain Analyses of Counterion and Solvent Effects

We have theoretically studied the non‐identity S_N2 reactions of M_nOH^(n?1)+CH₃Cl (M⁺=Li⁺, Na⁺, K⁺, and MgCl⁺; n=0, 1) in the gas phase and in THF solution at the OLYP/6‐31++G(d,p) level using polarizable continuum model (PCM) implicit solvation. We want to explore and understand the effect of the metal counterion M⁺ and solvation on the reaction profile and the stereoselectivity of these processes. To this end, we have explored the potential energy surfaces of the backside (S_N2‐b) and frontside (S_N2‐f) pathways. To explain the computed trends, we have carried out analyses with an extended activation strain model (ASM) of chemical reactivity that includes the treatment of solvation effects.     

A Mechanistic Study of the Utilization of arachno‐Diruthenaborane [(Cp*RuCO)2B2H6] as an Active Alkyne‐Cyclotrimerization Catalyst

The reaction of nido‐[1,2‐(Cp*RuH)₂B₃H₇] ( 1 a , Cp*=η⁵‐C₅Me₅) with [Mo(CO)₃(CH₃CN)₃] under mild conditions yields the new metallaborane arachno‐[(Cp*RuCO)₂B₂H₆] ( 2 ). Compound 2 catalyzes the cyclotrimerization of a variety of internal‐ and terminal alkynes to yield mixtures of 1,3,5‐ and 1,2,4‐substituted benzenes. The reactivities of nido‐ 1 a and arachno‐ 2 with alkynes demonstrates that a change in geometry from nido to arachno drives a change in the reaction from alkyne‐insertion to catalytic cyclotrimerization, respectively. Density functional calculations have been used to evaluate the reaction pathways of the cyclotrimerization of alkynes catalyzed by compound 2 . The reaction involves the formation of a ruthenacyclic intermediate and the subsequent alkyne‐insertion step is initiated by a [2+2] cycloaddition between this intermediate and an alkyne. The experimental and quantum‐chemical results also show that the stability of the metallacyclic intermediate is strongly dependent on the nature of the substituents that are present on the alkyne.     

High‐Performance Ru1/CeO2 Single‐Atom Catalyst for CO Oxidation: A Computational Exploration

By means of density functional theory computations, we examine the stability and CO oxidation activity of single Ru on CeO₂(111), TiO₂(110) and Al₂O₃(001) surfaces. The heterogeneous system Ru₁/CeO₂ has very high stability, as indicated by the strong binding energies and high diffusion barriers of a single Ru atom on the ceria support, while the Ru atom is rather mobile on TiO₂(110) and Al₂O₃(001) surfaces and tends to form clusters, excluding these systems from having a high efficiency per Ru atom. The Ru₁/CeO₂ exhibits good catalytic activity for CO oxidation via the Langmuir–Hinshelwood mechanism, thus is a promising single‐atom catalyst.     

DFT Study on the Electronic and Structural Properties of ReO5-/0 Clusters

The electronic and structural properties of ReO5 and ReO5 clusters are investigated using density functional theory (DFT) calculations. The lowest energy structures for both the anionic and neutral clusters are determined, and the corresponding photoelectron spectrum is simulated. Our results show that ReO5 can be described as an unusual peroxo molecule, Re(O)3(η2-O2) , while ReO5 is found to be exhibiting the O2 o radical character. Molecular orbital analyses and spin density analyses are performed to elucidate the chemical bonding and the electronic and structural properties in these two rhenium oxide clusters.     

Theoretical study of molecular and electronic structure of 2‐Se‐(2‐methyl‐2‐propenyl)‐1‐benzoic acid

A theoretical study of 2‐Se‐(2‐methyl‐2‐propenyl)‐1‐benzoic acid was carried out to investigate the molecular and electronic structure of this molecule, using the B3LYP density functional theory (DFT) method with the 6‐311+G** basis set. The optimized geometry of the molecule was obtained for the ortho, meta, and para isomers of the complex. In addition, the theoretical vibrational spectrum is presented, and thermal corrections in the limit of 100–1,000 K are discussed using the Shomate thermodynamic equations. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Probing for Structural Features of Boron‐rich Solids with EELS

Crystal structures of boron‐rich solids are characterized by boron atom arrangements that are quite diverse: chains, sheets, and a variety of polyhedra like octahedra, pentagonal bipyramids, cuboctahedra, and icosahedra are observed. Probing by electron energy‐loss spectroscopy (EELS), these different structural features are mirrored by a pronounced variation of the energy loss near‐edge fine structure (ELNES) of the B_K ionization edges. For identification, characteristics of these fine structures can be used as so‐called “coordination fingerprints”, which is shown for solids like MgB₂, TaB₂, ZrB₂, CaB₆, SrB₆, BaB₆, NaB₅C, KB₅C, Na₃B₂₀, Na₂B₂₉, UB₁₂, ZrB₁₂, LaB₂C₂, CeB₂C₂, and CaB₂C₂. In addition, theoretical calculations of ELNES based on the density functional theory (FLAPW method) are presented for an example of boron‐rich solids.