Organoplatinum(IV) tris-chelate complexes, each having a cyclic metallacarbonate ring: synthesis, characterization and kinetic studies of the formation

The complexes [Pt[(CH2)4](NN)], 1a (NN = 2,2'-bipyridine) and 1b (NN = 1,10-phenanthroline) react with 2,3-epoxypropylphenyl ether in the presence of CO2 to give tris-chelate platina(IV)cyclopentane complexes characterized by 1H and 13C NMR spectroscopy as [Pt[(CH2)4](CH2CHCH2OPhOCO2)(NN)], 2. The reactions proceed by the SN2 mechanism and the rates were independent of concentration of CO2. It is demonstrated that for 1a, the reaction proceeds 2.32 times faster than the similar reaction in which the dimethyl analog, [PtMe2(2,2'-bipyridine)], is used. The analog tris-chelate complex [Pt[(CH2)4](CH2CHPhOCO2)(phen)], 3a, was similarly synthesized.     

Formation of dimers of inclusion cryptand/paraquat complexes driven by dipole-dipole and face-to-face pi-stacking interactions

Dimers of inclusion complexes were formed from a new cryptand and viologens (paraquats) driven by dipole-dipole and face-to-face pi-stacking interactions as shown by mass spectrometric characterization and X-ray analysis.     

Direct syntheses of functionalized mesostructured silica by using an inexpensive silica source

The co-condensation of water soluble sodium silicate and different organotrialkoxysilanes in the presence of non-ionic triblock copolymers under acidic conditions provides a very convenient, general and economic one step synthesis methodology for the preparation of organically functionalised mesostructured silica.     

The decomposition of diazo-compounds induced by nucleophiles. The decomposition of 9-diazofluorene in the presence of hydroxide or alkoxide ions

9-Diazofluorene, on treatment with stoichiometric or substoichiometric amounts of quaternary ammonium hydroxide or methoxide or of potassium t-butoxide in solution in aqueous or alcoholic dimethyl sulfoxide or acetonitrile at 30 degrees C, decomposes with evolution of nitrogen to yield fluorenone azine [bis(fluorenylidene)hydrazine] in almost quantitative yield. Studies are reported of the identity of the minor by-products, together with an examination of the kinetics of the reactions and additional spectroscopic experiments. The general rate equation is v = k[FIN2]3/2[Nu-]1/2, where Nu- represents the nucleophile. It is concluded that the oxyanions, most probably after nucleophilic attack on 9-diazofluorene under these basic conditions to generate a new anionic species, are capable of transferring an electron to the diazo-compound. This initiates decomposition of further diazo-molecules in a process of electron-transfer chain catalysis that bears some similarities to, but has also some differences from, that encountered using cathodic initiation. In support of this interpretation it is found that reactions can be accelerated by the introduction of carbon acids (fluorene, 9-phenylfluorene) into the reaction mixtures. The nature of the initiation, propagation and termination steps of the chain mechanism are discussed.     

A commutativity criterion for certain algebras of invariant differential operators on nilpotent homogeneous spaces

Let G be a connected, simply connected real nilpotent Lie group with Lie algebra , H a connected closed subgroup of G with Lie algebra and f a linear form on satisfying f([, ]) = {0} Let _f be the unitary character of H with differential at the origin. Let _f be the unitary representation of G induced from the character _f of H. We consider the algebra (, , f) of differential operators invariant under the action of G on the bundle with basis G/H associated to these data. We show that (, , f) is commutative if and only if _f is of finite multiplicities. This proves a conjecture of Corwin-Greenleaf and Duflo. Mathematics Subject Classification (1991):43A80, 43A85, 22E25, 22E27, 22E30UMR n 7539 du CNRS, Analyse, Géométrie et Applications.UMR n 7586 du CNRS, Théorie des Groupes, Représentations, Applications.     

Intransitive Permutation Group with Bounded Movement

Let G be a intransitive permutation group on a set with no fixed point in ; let m, n be a positive integer and let |^g – | m, for every and g G. When G has t orbits and degree n close to [2mp/(p – 1)] + t – 1, this paper constructs such a group with m close to [n(p – 1)/2p].AMS Subject Classification: 20BXX.     

Metric and Complete Metric σ-Frames

A -frame is a lattice in which countable joins exist and binary meets distribute over countable joins. In this paper, the category MFrm, of metric -frames, is introduced, and it is shown to be equivalent to the category MLFrm _u, of metric Lindelöf frames.Finally, it is shown that the complete metric -frames are exactly the cozero parts of complete metric Lindelöf frames.     

Precision of degree of polarization estimation in the presence of additive Gaussian detector noise

We address the problem of degree of polarization (DOP) estimation in images limited by additive Gaussian detector noise. We derive and analyze the probability density function (PDF) of the pixelwise DOP estimate, which is shown to have significantly different statistical properties than when noise is Gamma distributed (speckle). We then determine the Cramer-Rao Lower Bound and the maximum likelihood estimator of the DOP. We deduce from this study practical solutions for characterizing and reducing the noise in these images.     

Armatans A and B,New Antimicrobial Isoflavans from Colutea armata

Chemistry of Natural Compounds - Armatans A (1) and B (2), new isoflavans, have been isolated from the EtOAc-soluble fraction of the MeOH extract of Colutea armata Hemsl. & Lace, along with...     

Synthesis and microstructural study of stereoblock elastomeric polypropylenes from metallocene catalyst (2‐PhInd)2ZrCl2 activated with cocatalyst mixtures

Various elastomeric polypropylenes (PPs) are synthesized through homogeneous propylene polymerization with metallocene catalyst (2‐PhInd)₂ZrCl₂ in the presence of different cocatalyst mixtures: triethylaluminum (TEA)/methylaluminoxane (MAO) or triisobutylaluminum (TIBA)/MAO in the range of Al_AlR3/Al_MAO = 0.0–0.9. The cocatalyst formulation impacts the resultant polymer microstructure and the thermal and dynamic mechanical properties of the produced PPs. ¹³C NMR analysis of the polymers reveals essentially atactic PP, with mmmm = 7.9%, when Al_AlR3/Al_MAO = 0.0. The mmmm pentad content is maximized when Al_AlR3/Al_MAO = 0.8; for TIBA, mmmm = 23.5%; and for TEA, mmmm = 17.6%. Differential scanning calorimetry analysis and dynamic mechanical thermal analysis corroborate these findings. Specifically, T_m, ΔH_m, and T_g are essentially maximized under these conditions, and the minimum damping is observed for Al_AlR3/Al_MAO = 0.6–0.8. ¹H NMR analysis of the mixtures of catalyst and cocatalysts (without monomer) shows very minor differences for [Zr]:Al_AlR3 in the range of 1:1–1:5. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013