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1.
Elke Barsties Stefan Schaible Marc-Heinrich Prosenc Ursula Rief Werner Rll Oliver Weyand Birgit Dorer Hans-Herbert Brintzinger 《Journal of organometallic chemistry》1996,520(1-2):63-68
Bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (2-(CH3)2N-C9H6)2ZrCl2, and dimethylsilyl-bridged bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (CH3)2Si(2-(CH3)2N-C9H5)2ZrCl2, were prepared by reaction of the corresponding ligand lithium salts with ZrCl4 in toluene. Diffractometric structure determinations reveal C2-symmetric complex geometries for both complexes. An increased electron density at the Zr center of the dimethylamino-substituted complexes is indicated by reduction potentials which are 0.3–0.4 V more negative than those of their unsubstituted analogs. When activated with methyl aluminoxane in toluene solution, (CH3)2Si(2-(CH3)2N-C9H5)2ZrCl2 catalyzes the polymerization of propene to polymers with a microstructure comparable with that of polymers produced with other Me2Si-bridged bis(indenyl)ZrCl2 complexes, but with a substantially increased fraction of i-propyl end groups derived from alkyl exchange between Zr-polymer and Al---Me species. 相似文献
2.
The varying -bonding contributions in the title compounds caused by the different electronic and molecular structure of the chelate rings are used for explaining the large band splittings in the absorption spectra by trigonal symmetry. It is shown that usual ligand field theory and the angular overlap model are not able to account for the trigonal level splitting of Cr(acac)3 for which the coordination sphere of oxygen atoms is nearly octahedrally arranged. The experimental finding can, however, be rationalized by an extended angular overlap model which considers the phase coupling of -orbitals in the ligands leading to non-additive contributions to the metal-ligand bond energy.On leave of absence from the Bulgarian Academy of Sciences, Sofia, Bulgaria 相似文献
3.
In a study of the reaction system MAO/(C5H5)2ZrMe2, the size of the ion pair [(C5H5)2Zr(mu-Me)2AlMe2]+ [Me-MAO]- was determined by pulsed field-gradient NMR of its cationic moiety. A mean effective hydrodynamic radius of 12.2-12.5 A, determined from diffusion rates in benzene solution at different zirconocene and MAO concentrations, indicates that the ion pair remains associated even at the lowest concentrations studied. At elevated concentrations, aggregation to ion quadruples or higher aggregates is indicated by an apparent size increase and by shifts of the C5H5 and Me 1H NMR signals. The equilibrium constant for the reaction [(C5H5)2ZrMe+...Me-MAO-] + 1/2Al2Me6 right harpoon over left harpoon [(C5H5)2Zr(mu-Me)2AlMe2]+ [Me-MAO]- changes at different Al/Zr ratios; this indicates that MAO contains various species that produce Me-MAO- anions with different Lewis basicities. The volume of the Me-MAO- anion suggests that it contains 150-200 Al atoms. 相似文献
4.
Stephan Jüngling Rolf Mülhaupt Udo Stehling Hans-Herbert Brintzinger David Fischer Franz Langhauser 《Journal of polymer science. Part A, Polymer chemistry》1995,33(8):1305-1317
Propene was polymerized at 40°C and 2-bar propene in toluene using methylalumoxane (MAO) activated rac-Me2Si(Benz[e]Indenyl)2ZrCl2 ( BI ) and rac-Me2Si(2-Me-Benz[e]Indenyl)2ZrCl2 ( MBI ). Catalyst BI /MAO polymerizes propene with high activity to afford low molecular weight polypropylene, whereas MBI /MAO is less active and produces high molecular weight polypropylene. Variation of reaction conditions such as propene concentration, temperature, concentration of catalyst components, and addition of hydrogen reveals that the lower molecular weight polypropylene produced with BI /MAO results from chain transfer to propene monomer following a 2,1-insertion. A large fraction of both metallocene catalyst systems is deactivated upon 2,1-insertion. Such dormant sites can be reactivated by H2-addition, which affords active metallocene hydrides. This effect of H2-addition is reflected by a decreasing content of head-to-head enchainment and the formation of polypropylene with n-butyl end groups. Both catalysts show a strong dependence of activity on propene concentration that indicates a formal reaction order of 1.7 with respect to propene. MBI /MAO shows a much higher dependence of the activity on temperature than BI /MAO. At elevated temperatures, MBI /MAO polymerizes propene faster than BI /MAO. © 1995 John Wiley & Sons, Inc. 相似文献
5.
Gerd Eyring Thomas Schönherr Hans -Herbert Schmidtke 《Theoretical chemistry accounts》1983,64(2):83-96
The 90 K diffuse reflectance spectra of some octahedral Rh(III), Ir(III) and Pt(IV) complex compounds with chloride, thiocyanate and amine ligands are reported. The spectra show in the visible and near ultraviolet distinct bands due to spin-orbit components of singlet-triplet d-d transitions which are explained by ligand field calculations including spin-orbit coupling considering all possible d-electron configurations. Model parameter sets are obtained by fitting the measured band peaks to possible transitions between calculated energy levels. For some of the bands the vibrational structure could be resolved which is assigned to metal-ligand stretching vibrations of the electronically excited complex octahedra with vibrational fundamentals lower than those of the ground state. 相似文献
6.
Bond energy contributions calculated from first and second order density matrix terms as partitioned by Ruedenberg's procedure have been obtained for HeH+ in the ground state and in the first excited 1Σ+. For the chemically bonded ground state the full partitioning is investigated for all internuclear distances R. The wavefunctions used for calculating the density matrices are obtained from an SCF calculation at near Hartree-Fock quality, using Slater orbitals with exponents which for each R are optimized simultaneously with the coefficients. For the excited state a limited CI has been performed. The results for promotional, charge transfer, and interference terms for kinetic and potential bond contributions are presented in the form of energy plots E(R). Starting from the promoted atoms and subsequently allowing for charge transfer the importance of the electron interaction is demonstrated by the unusually low quasiclassical electron repulsion curve due to electronic charge transfer, which makes an essential contribution to the decrease in energy during bond formation. 相似文献
7.
For purposes of interpreting broad band electronic spectra of complexes, the 3N-5 dimensional potential energy hypersurface may be reduced substantially. Consideration of the geometry of the orbital transition involved allows selection of an appropriate cross section, depending on which features should be represented. In addition, the orbital transition geometry predicts which vibrational modes will contribute significantly to the width of the spectrum. In the particular case of the first and second spin-allowed bands in d3 and d6 complexes, α1g and ?g modes are responsible for the band width. 相似文献
8.
Hans-Herbert Schmidtke 《Theoretical chemistry accounts》1967,8(5):376-382
The virial theorem for various not necessarily homogeneous potential functions V(r) is derived. It is proved in a transparent way that approximate wave functions at optimal scale satisfy the general virial theorem for any radial potential V(r). The proposed method for improving a variational wave function which by the scaling procedure obeys the virial theorem is tested in the case of some simple screened coulomb potentials.
Zusammenfassung Das Virialtheorem für verschiedene, nicht unbedingt homogene Potentialfunktionen V(r) wird abgeleitet. Es wird gezeigt, da\ eine NÄherungsfunktion mit optimalem Skalenparameter auch das allgemeine Virialtheorem für beliebige Radialpotentiale V(r) erfüllt. Die Methode der Streckung des Grundgebietes (scaling) dient zur Verbesserung von NÄherungsfunktionen, was am Beispiel einiger abgeschirmter Coulomb-Potentiale demonstriert wird.
Résumé Le théorème du viriel pour quelques fonctions de potentiel V(r) non nécessairement homogènes est dérivé du théorème général. Il est prouvé d'une manière intuitive que des fonctions d'onde approchées, à l'échelle optimum, satisfont le théorème du viriel général pour tous les potentiels radiaux V(r). La méthode proposée pour améliorer une fonction d'onde variationnelle, qui obéit au théorème du viriel, est essayée dans le cas de quelques simples potentiels coulombiens écrantés.相似文献
9.
Darstellung und Charakterisierung einige Thiocyanat- und Selenocyanat-Komplexe von Übergangsmetallen
Some 6:1 thiocyanate complexes of FeIII, MoIII, RuIII, OsIII, IrIII and some 6:1 or 4:1 selenocyanate complexes of FeII, FeIII, MoIII, RhIII, PdII, PtII, and AuIII have been prepared as salts of large organic cations. The compounds are characterized by their infra-red spectra and by conductance measurements. In particular the linkage property of the thiocyanate and selenocyanate ligand is discussed together with the consequences it has on the AHRLAND -CHATT -DAVIES -PEARSON classification of the central ions. 相似文献