Photooxidation of some metallocenes in a polymer matrix

The changes in the electronic absorption spectra (UV-Vis) of some metallocene-doped poly(methyl methacrylate) (PMMA) thin films containing chloroform molecules as impurities were studied after photoexcitation in the nitrogen atmosphere. Photoexcitations were made by monochromatic radiation (using a Xe-lamp source and a monochromator) at an interval of few nanometers in the spectral range 210-750 nm. The changes in spectra were studied as a function of photoexcitation time (duration), amount of metallocene in the film and the amount of chloroform molecules present in the film. Occurrence of photoinduced charge-transfer between some metallocenes and chloroform molecules confined in the PMMA thin films was observed, which indicated photooxidation of the metallocenes in the polymer matrix. Photoresponse in the case of ferrocene derivatives was observed to decrease with the increase in the value of para- Hammett constant for the substituent attached to the ferrocene unit and also with increasing half-wave potential for the ferrocene derivatives. Photoeffects on the metallocenes having different central metal atom were studied and it was noticed that the photoeffects on the metallocenes with "18 valence electrons", as in ferrocene and ruthenocene, favored the occurrence of photoinduced charge-transfer between the metallocene and chloroform molecules present in a PMMA film. The photooxidation of a metallocene in a PMMA thin film resulted in an enhanced photoconductivity of the polymeric film.     

Photoinduced charge-transfer between ferrocene derivatives and chloroform molecules confined in poly(methyl methacrylate) thin films

The changes in the electronic absorption spectra (UV-Vis) (after photoexcitations) of poly(methyl methacrylate) (PMMA) thin films doped with a ferrocene derivative and containing chloroform molecules as impurities, have been studied as a function of photoexcitation wavelength (210–750 nm), photoexcitation time (duration), amount of ferrocene derivative in the film and amount of chloroform molecules present in the film. Occurrence of photoinduced charge-transfer between some ferrocene derivatives and chloroform molecules confined in the PMMA thin films has been observed. The effects of the substitution group (attached to the ferrocene unit) on the photoinduced changes are discussed.     

Fluctuations in absorbance observed for photoexcited ferrocene-doped poly(methyl methacrylate) thin films containing chloroform molecules as impurities

The time-dependent changes in absorbance in the case of ferrocene-doped poly(methyl methacrylate) thin films containing chloroform molecules have been investigated after photoexcitation in nitrogen atmosphere. Photoexcitations have been made by the monochromatic light (using Xe-source and a monochromator) in the UV range. An increase in absorbance associated with spectacular fluctuations in its value, has been noticed. The nature of the variation in the fluctuations has been studied as a function of time (duration) of photoexcitation, photoexcitation wavelength and concentration of ferrocene in the film. The observed results have been discussed considering the role of secondary reaction after photoexcitation as well as the diffusion of small chemical species in the polymer matrix.     

Thorium oxo and sulfido metallocenes: synthesis, structure, reactivity, and computational studies

The synthesis, structure, and reactivity of thorium oxo and sulfido metallocenes have been comprehensively studied. Heating of an equimolar mixture of the dimethyl metallocene [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)ThMe(2) (2) and the bis-amide metallocene [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)Th(NH-p-tolyl)(2) (3) in refluxing toluene results in the base-free imido thorium metallocene, [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)Th═N(p-tolyl) (4), which is a useful precursor for the preparation of oxo and sulfido thorium metallocenes [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)Th═E (E = O (5) and S (15)) by cycloaddition-elimination reaction with Ph(2)C═E (E = O, S) or CS(2). The oxo metallocene 5 acts as a nucleophile toward alkylsilyl halides, while sulfido metallocene 15 does not. The oxo metallocene 5 and sulfido metallocene 15 undergo a [2 + 2] cycloaddition reaction with Ph(2)CO, CS(2), or Ph(2)CS, but they show no reactivity with alkynes. Density functional theory (DFT) studies provide insights into the subtle interplay between steric and electronic effects and rationalize the experimentally observed reactivity patterns. A comparison between Th, U, and group 4 elements shows that Th(4+) behaves more like an actinide than a transition metal.     

Charge-transfer spectra of ferrocene in halocarbon solvents under photoexcitation

The changes in the electronic absorption spectra of ferrocene in the halocarbon solvents chloroform and carbontetrachloride have been investigated under photoexcitation in nitrogen atmosphere. Photoexcitations have been made with monochromatic light (using an Xe-source and a monochromator), at intervals of a few nanometers in the spectral range 220–750 nm. Analysing the spectra by a modified method the position of the charge-transfer-to-solvent (CTTS) band has been located for both the solvents. The position of the CTTS band in the case of carbontetrachloride solution located (320 nm) by the present study is different from the previously reported value (307 nm), while from the previous studies the position of the CTTS band in the case of the spectra of ferrocene in chloroform was not clear. From the present investigation, the changes in spectra after photoexcitation studied as a function, the concentration of ferrocene in the solution and the time (duration) of photoexcitations, have been observed to be systematic. Using the position of the new band (320 nm) for the CTTS transition in the case of carbontetrachloride, ionization potential of ferrocene has been estimated and the estimated value has shown excellent agreement with the experimental value indicating the exactness of the newly located CTTS band position.     

The influence of the transition metal and the heteroatomic-bridge on the action of metallocene/methyl aluminoxane catalysts in ethylene polymerization and on the properties of the polymer

This work reports a comparative study of the catalytic behaviour for a series of metallocenes derived from Ti, Zr, Hf and Nb, which after activation with methylaluminoxane can polymerize ethylene. Results show that the Zr metallocene with a  (CH₃)₂Si Bridge presents the highest activity, and the metallocenes based on Hf and Nb do not show any significant activity under the tested conditions.     

Density-functional calculations of relativistic spin-orbit effects on nuclear magnetic shielding in paramagnetic molecules

Terms arising from the relativistic spin-orbit effect on both hyperfine and Zeeman interactions are introduced to density-functional theory calculation of nuclear magnetic shielding in paramagnetic molecules. The theory is a generalization of the former nonrelativistic formulation for doublet systems and is consistent to O(alpha4), the fourth power of the fine structure constant, for the spin-orbit terms. The new temperature-dependent terms arise from the deviation of the electronic g tensor from the free-electron g value as well as spin-orbit corrections to hyperfine coupling tensor A, the latter introduced in the present work. In particular, the new contributions include a redefined isotropic pseudocontact contribution that consists of effects due to both the g tensor and spin-orbit corrections to hyperfine coupling. The implementation of the spin-orbit terms makes use of all-electron atomic mean-field operators and/or spin-orbit pseudopotentials. Sample results are given for group-9 metallocenes and a nitroxide radical. The new O(alpha4) corrections are found significant for the metallocene systems while they obtain small values for the nitroxide radical. For the isotropic shifts, none of the three beyond-leading-order hyperfine contributions are negligible.     

Ethyl‐iso‐butylaluminoxane activated metallocene catalyst for olefin polymerization

Ethylene and propylene were polymerized by different combinations of metallocenes and aluminoxanes. Ethyl‐iso‐butylaluminoxane (EBAO), which could be easily obtained by direct hydrolysis of Et₃Al/iso‐Bu₃Al in toluene with water, displayed as good polymerization activity as methylaluminoxane when it was paired with some metallocenes. The UV–visible spectroscopic study on different metallocene/aluminoxane pairs suggests that tightness of the ionic pairs generated from the reaction between metallocene and aluminoxane is different for a fixed metallocenium. The loose ionic pair derived from EBAO prefers the monomer propagation and hinders the interaction between active species, which results in high catalytic activity and molecular weight. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 998–1003, 2003     

Polymerization of olefins in the presence of metal powders with homogeneous catalysts

Homogeneous catalysts based on metallocenes/methylaluminoxane are totally absorbed on surfaces of different metals. Because the methylaluminoxane is relatively stable against small molecules such as water covering metal surfaces, the aluminoxane can be fixed on powders without losing its activity. After treatment with the metallocene, active sites are only formed on the surface of the fillers. Upon injection of the olefins they are polymerized in the presence of the metals. Olefins such as ethene and propene, and cycloolefins or dienes, are used.     

Ferromagnetism in Metallocene-Doped Fullerenes

 Ferromagnetism in fullerene-based systems doped with metallocenes is reviewed. These compounds form a ferromagnetic state by spin-coupling between π electrons on fullerene units, while the metallocene molecules do not contribute to the spin ordering. One of these compounds has the highest critical temperature (19 K) for this class of compound. The magnetic properties of these materials are very strongly dependent on the crystallization conditions.     

Hydrogen transfer reactions of supported metallocene catalysts

The evolution of methane from methylaluminoxane (MAO) solutions is enhanced in the presence of homogeneous metallocenes. This reaction serves as a model for the deactivation of metallocene catalysts. By supporting different metallocenes on a silica/MAO carrier the deactivation reaction by alpha-hydrogen transfer among metallocene active sites and aluminum alkyls can be suppressed. The suppression of alpha-hydrogen transfer is proven for different Al/Zr ratios and by near independence of the polymerization activity on the catalyst aging time, after reaching maximum activity. Aluminum alkyls and MAO leach Cp₂ZrCl₂ from the carrier, the leached metallocene is only active in polymerization if MAO is present.     

Highly isospecific,immobilized zirconocene catalysts supported on chemically modified SiO2

Most of the supported metallocene catalysts reported so far have been devised to immobilize metallocenes on the solid surface utilizing the ionic interactions between metallocenes and surface active sites. Whereas, we have been challenging to prepare more rigidly immobilized catalysts by using the chemically modified SiO₂. The SiO₂-supported zirconocene catalysts thus prepared could be activated by ordinary trialkylaluminiums like Al(i-C₄H₉)₃ to give highly isotactic polypropene (PP) with high melting temperature (Tm) and number-average molecular weight (Mn). This paper summarizes the results obtained so far.     

Electronic structures of mixed-sandwich complexes of cyclopentadienyl and Hydrotris(pyrazolyl)borate ligands with 3d transition metals

The electronic and magnetic properties of a series of mixed-sandwich complexes MCp(R)Tp (Cp(R) = Cp or Cp; Tp = hydrotris(pyrazolyl)borate; M = V, Cr, Fe, Co or Ni) have been studied and compared to their homoleptic analogues, MCp(R)(2) and MTp(2). Solid-state magnetic susceptibility measurements and EPR spectroscopic data indicate that complexes with d(3), d(6), and d(8) configurations are similar electronically to their metallocene analogues, except for FeCpTp, which displays a spin equilibrium (S = 0 if S = 2) in solution which was investigated by variable- temperature NMR spectroscopy. The d(2) complex [VCpTp](+) displays magnetic behavior consistent with an orbitally nondegenerate ground state. The d(4) species CrCpTp has a high-spin (S = 2) ground state. The d(7) species CoCpTp is high spin (S = 3/2) whereas its Cp analogue and [NiCpTp](+) are both low-spin (S = 1/2) species. The optical spectra of the d(3), d(6), and d(8) complexes were assigned in a fashion similar to the analogous metallocenes and ligand-field parameters (delta(1) = delta-sigma gap, delta(2) = sigma-pi gap for d-orbitals in axial symmetry) calculated. The analysis shows that for 15-electron species the total ligand-field splitting, delta(TOT), is larger than for their metallocene analogues, whereas for the 18-electron case Delta(TOT) is smaller and for 20-electron systems delta(TOT) is approximately the same. In all cases delta(2) is substantially reduced compared to the metallocenes, and in the majority of cases delta(1) is markedly larger. DFT calculations were performed to investigate further the nature of the ligand environment on the frontier orbitals in these complexes. Orbital energies and compositions were calculated and compared for a series of homoleptic and mixed-sandwich complexes of Ni(II) and across the 1st transition series for MCp(R)Tp species. The ability of Tp (vs Cp) to act as a delta-donor (with respect to the principal molecular axis) imparts significant ligand antibonding character to the delta-orbitals and results in decreased epsilon(pi)-epsilon(delta) values compared to the metallocenes and an increased tendency toward high-spin complexes in the mixed-sandwich complexes. Structure calculations were performed for CrCpTp, [VCpTp](+), and CoCpTp which show substantial distortions from ideal axial symmetry in their crystal structures. The origins of these distortions were confirmed to arise from unequal occupancy of near-degenerate delta- and pi-levels.     

Recent advances in olefin polymerization

Various metallocenes were tested for syndiotactic polymerization of propylene. Reduction in the amount of costly methylalumoxane (MAO) or replacement with the other components was accomplished. Small modifications in the metallocene ligands brought about remarkable differences in the resulting catalysts concerning their storage stability, H₂ response as well as stereo-specificity. Syndiotactic polypropylene (SPP) in the melt state behaves very differently compared to isotactic polypropylene (IPP). The notion that these polymers have different distributions of molecular entanglements are pursued, and verified for the first time. Excellent dispersibility of other olefin polymers in SPP matrix contributed to improve the usefulness of SPP.     

Ferromagnetism in Metallocene-Doped Fullerenes

 Ferromagnetism in fullerene-based systems doped with metallocenes is reviewed. These compounds form a ferromagnetic state by spin-coupling between π electrons on fullerene units, while the metallocene molecules do not contribute to the spin ordering. One of these compounds has the highest critical temperature (19 K) for this class of compound. The magnetic properties of these materials are very strongly dependent on the crystallization conditions. Corresponding author. E-mail: Dragan.Mihailovic@ijs.si Received September 4, 2002; accepted September 6, 2002     

由富烯配体合成茂金属化合物的研究

报道了一系列富烯包括烷基取代富烯、6-氨基富烯和具有稠环结构的6-氨基苯并富烯经由去氢或加成反应合成取代二茂金属络合物;(1-二甲氨基)乙烯基环戊二烯基锂与过渡金属的络合反应在一定条件下可以发生分子内碳碳偶联及二甲基胺的消除反应,得到丙烯桥联茂金属化合物,从推导的反应历程提出该反应的反应机理;尚合成了两个新的外消旋手性化合物。     

Polymerization of propylene by mixed Ziegler–Natta and metallocene catalysts

The polymerization of propylene using a mixture of racemic metallocenes and Ziegler–Natta catalysts was investigated. The polypropylene was obtained as a mixture of a fine powder and beads, with the powder being absorbed partially on the beads. The relative amount of the powder can be controlled by the concentration of the metallocene. The compatibility between the components of the mixed catalytic systems and the effect of the components on the rate of polymerization and on the properties of the new polymers were studied. The metallocene system dramatically affects the melt viscosity, isotacticity and molecular weight of the polymers. The two catalytic systems are able to act jointly, producing different polymers, for which separate melting and crystallization temperatures are obtained. © 1998 John Wiley & Sons, Ltd.     

Mechanistic aspects of the olefin polymerization with metallocene catalysts

With C₁-, C₂- or C_s-symmetric metallocenes, different intermediates and types of copolymers can be obtained from randomly distributed to alternating structures. Substitution of the Cp-ring in [Me₂C-(tert-Bu Cp)(Flu)]ZrCl₂ yields ethene/norbornene copolymers with an alternating structure, because the rigid norbornene can only be inserted from the open side of the metallocene. By variation of the polymerization parameters, copolymers with glass transition temperatures above 180°C and molecular weights > 100 000 are synthesized. By supporting different metallocenes on a silica/methylaluminoxane (MAO) carrier the deactivation reaction under electron and hydrogen transfer can be suppressed. This is proved for different Al/Zr ratios when trimethylaluminum (TMA) is used as cocatalyst by the lack of methane evolution by metallocenes and by near independence of the polymerization activity on the prereaction time, after reaching maximum activity. Aluminumalkyls and MAO leach Cp₂ZrCl₂ from the carrier, the leached metallocene is only active in polymerization by adding MAO.     

Molecular modeling on the prediction of silolene‐bridged indenyl metallocene catalysts for isotactic polypropylene

Two new silolene‐bridged metallocenes for isotactic polypropylene, racemic (1,4‐butanediyl) silylene‐bis (1‐η⁵‐2‐methyl‐indenyl) dichlorozironium and racemic diphenyl silylene‐bis (1‐η⁵‐2‐methyl‐indenyl) dichlorozironium, were designed in terms of the mechanism and concept of the activity and selectivity of metallocenes. The predictions on which the designs were based were carried out for four metallocene catalysts through molecular modeling methods such as molecular mechanics and charge equilibrium. In a comparison of the data from three of the catalysts that were successfully synthesized, the predicted orders of the activity and selectivity were consistent. This shows that classical methods such as charge equilibrium are useful in predicting the activity of catalysts. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2232–2238, 2000     

Morphology Control in Metallocene Polymerization; Organic Supports vs. Non-aqueous Emulsion Polymerization

Nano-sized latex support in metallocene polymerization is known to be able to avoid fuming or leaching and leads to a powder-like and well-processable polymer. Focus has been put on the fragmentation behaviour of the particles, a key parameter to morphology control. To study the different behaviour of the new systems as classical inorganic supported metallocenes, e.g. SiO₂, a wide range of analytical methods were applied. Fluorescence microscopy, polymerization videomicroscopy, as well as kinetic studies led to a better understanding of the process. The performance of the supports was approved by several phenoxy-imine type catalysts (“FI-Catalyst”), which were combined with a tailored latex support. Ultra high molecular weight polyethylene (UHMWPE) was synthesized without any reactor fouling thereby. A different approach towards the metallocene catalyzed olefin polymerization is also presented. Based on emulsion polymerization, it enables very good control over product morphology. The completely hydrophobic system consists of perfluorinated solvent as a continuous phase and a hydrocarbon solvent as a dispersed phase. In contrast to the already existing water based emulsion polymerization of olefins, very high molecular weights are achieved.