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101.
Pavan Mathur 《Journal of Chemical Sciences》2006,118(6):553-568
New tetradentatebis-benzimidazole ligands have been synthesized and utilized to prepare copper (II) complexes. Some of these copper (II) complexes
have been characterized structurally. The copper (II) in these complexes is found to possess varying geometries. A distorted
octahedral geometry is found with a highly unsymmetrical bidentate nitrate group. An unusual polymeric one-dimensional structure
is observed where copper (II) is in a distorted square pyramidal geometry with a monodentate nitrate ion, having long Cu-O
bond, while a distorted triagonal bipyramidal geometry is found with two carbonyl O atoms and a Cl atom in the equatorial
plane, and two benzimidazole imine N atoms occupy the axial position. These compounds are found to activate the cumylperoxyl
group, and this has been utilized in the facile oxidation of aromatic alcohols to aldehydes, where they act as catalysts with
large turnovers. The yields of the respective products vary from 32 to 65%. The role of molecular oxygen has been studied
and an attempt has been made to identify the “active copper species”. Activation of molecular oxygen has also been observed
and has been used for oxidative dealkylation of a hindered phenol, producing di-butyl quinones with yields of 20–25% and 10–12
fold catalytic turnover. Dihydroxybenzenes and substituted catechols are also readily oxidized to the corresponding quinones,
in oxygen-saturated solvents. Yields of 84% have been observed with 34-fold catalyst turnover, with di-t-butylcatechol. The activity of these copper (II) —bis-benzmidazolediamide compounds is reminiscent of the functioning of copper centres in galactose oxidase, tyrosinase and catechol
oxidase. 相似文献
102.
Alexander Zeller 《Journal of organometallic chemistry》2006,691(21):4379-4385
The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (kH/kD = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active. 相似文献
103.
D. J. Plazek C. A. Bero S. Neumeister G. Floudas G. Fytas K. L. Ngai 《Colloid and polymer science》1994,272(11):1430-1438
By making creep and recoverable creep measurements of a nearly monodisperse low molecular weight poly(methyl phenyl siloxane) sample, we have found on decreasing temperature towardsT
g that there is continuously a change in the viscoelastic spectrum concomitant with a decrease of the steadystate recoverable compliance. This behavior is exactly the same as previously observed in low molecular weight poly(styrene), proving that this spectacular anomaly in the viscoelasticity of low molecular weight polymers is general and deserves an explanation. Photon correlation spectroscopic measurements performed on the same sample have extended the observation of the viscoelastic response to shorter times and the result corroborates the trend of variation established by the creep data.Dedicated to Prof.Dr. E. W. Fischer on his 65th Birthday. Prof.Dr. Fischer is known for his valuable contribution to fosterine, international collaboration of research in polymer science. This work is an example of his contribution because it would not be possible without him bringing us together. One of us (KLN) would like to take this opportunity to thank Prof. Dr. Fischer for his unwaiving support of the 1st (Crete) and the 2nd (Alicante) International Discussion Meeting on Relaxations in Complex Systems 相似文献
104.
We prove that to most of the known hypercyclic operators A on separable Banach spaces there exist compact (compact convex, compact connected) subsets K of E such that each compact (compact convex, compact connected) subset of E can be approximated with respect to Hausdorff's distance by for suitable .
Received July 8, 1997, in final form October 17, 1997 相似文献
105.
106.
Boundedness of commutators on homogeneous Herz spaces 总被引:9,自引:0,他引:9
The boundedness on homogeneous Herz spaces is established for a large class of linear commutators generated by BMO(R
n
) functions and linear operators of rough kernels which include the Calderón-Zygmund operators and the Ricci-Stein oRfiUatory
singular integrals with rough kernels.
Project supponed in pan by the National h’atural Science Foundation of China (Grant No. 19131080) and the NEDF of China. 相似文献
107.
Nobuaki Obata 《Acta Appl Math》1997,47(1):49-77
A general theory of operators on Boson Fock space is discussed in terms of the white noise distribution theory on Gaussian space (white noise calculus). An integral kernel operator is generalized from two aspects: (i) The use of an operator-valued distribution as an integral kernel leads us to the Fubini type theorem which allows an iterated integration in an integral kernel operator. As an application a white noise approach to quantum stochastic integrals is discussed and a quantum Hitsuda–Skorokhod integral is introduced. (ii) The use of pointwise derivatives of annihilation and creation operators assures the partial integration in an integral kernel operator. In particular, the particle flux density becomes a distribution with values in continuous operators on white noise functions and yields a representation of a Lie algebra of vector fields by means of such operators. 相似文献
108.
Peter Imkeller 《Probability Theory and Related Fields》1996,106(1):105-135
Summary. The analytic treatment of problems related to the asymptotic behaviour of random dynamical systems generated by stochastic
differential equations suffers from the presence of non-adapted random invariant measures. Semimartingale theory becomes accessible
if the underlying Wiener filtration is enlarged by the information carried by the orthogonal projectors on the Oseledets spaces
of the (linearized) system.
We study the corresponding problem of preservation of the semimartingale property and the validity of a priori inequalities
between the norms of stochastic integrals in the enlarged filtration and norms of their quadratic variations in case the random
element F enlarging the filtration is real valued and possesses an absolutely continuous law. Applying the tools of Malliavin’s calculus,
we give smoothness conditions on F under which the semimartingale property is preserved and a priori martingale inequalities are valid.
Received: 12 April 1995 / In revised form: 7 March 1996 相似文献
109.
Masaaki Sugihara 《Numerische Mathematik》1997,75(3):379-395
Summary. In the light of the functional analysis theory we establish the optimality of the double exponential formula. The argument
consists of the following three ingredients: (1) introduction of a number of spaces of functions analytic in a strip region
about the real axis, each space being characterized by the decay rate of their elements (functions) in the neighborhood of
the infinity; (2) proof of the (near-) optimality of the trapezoidal formula in each space introduced in (1) by showing the
(near-) equality between an upper estimate for the error norm of the trapezoidal formula and a lower estimate for the minimum
error norm of quadratures; (3) nonexistence theorem for the spaces, the characterizing decay rate of which is more rapid than
the double exponential.
Received September 15, 1995 / Accepted December 14, 1995 相似文献
110.
We investigate congruence classes and direct congruence classes of m-tuples in the complex projective space ℂP
n
. For direct congruence one allows only isometries which are induced by linear (instead of semilinear) mappings. We establish
a canonical bijection between the set of direct congruence classes of m-tuples of points in ℂP
n
and the set of equivalence classes of positive semidefinite Hermitean m×m-matrices of rank at most n+1 with 1's on the diagonal. As a corollary we get that the direct congruence class of an m-tuple is uniquely determined by the direct congruence classes of all of its triangles, provided that no pair of points of
the m-tuple has distance π/2. Examples show that the situation changes drastically if one replaces direct congruence classes by
congruence classes or if distances π/2 are allowed. Finally we do the same
kind of investigation also for the complex hyperbolic space ℂH
n
. Most of the results are completely analogous, however, there are also some interesting differences.
Received: 15 January 1996 相似文献