Preliminary communicationCatalytic olefin hydrogenation with nonacarbonyltris(triphenylphosphine)triruthenium and its derivatives. Crystal structure of [Ru2(CO)5(PPh3)(μ-PPh2)(μ-OCPh)]

The complexes [Ru₃(CO)₇(PPh₂)₂(C₆H₄)] and [Ru₂(CO)₅(PPh₃)(μ-PPh₂)(μ-OCPh)] were obtained by pyrolysis of [Ru₃(CO)₉(PPh₃)₃] and tested as catalysts for the hydrogenation of cyclohexene and 2-cyclohexen-1-one. The structure of [Ru₂(CO)₅(PPh₃)(μ-PPh₂)(μ-OCPh)] was established by a single crystal X-ray diffraction study.     

Sulfur bridging interactions of cis-planar NiII-S2N2 coordination units with nickel(II), copper(I,II), zinc(II), and mercury(II): a library of bridging modes, including NiII(micro2-SR)2MI,II rhombs

Sulfur bridging interactions between three cis-planar NiII-S2N2 complexes and NiII, CuI,II, ZnII, and HgII reactants were investigated by synthesis and X-ray crystal structures of some 24 complexes. This work was stimulated by recent crystallographic structures of the A-cluster of carbon monoxide dehydrogenase/acetylcoenzyme A synthase. This bridged biological assembly has the minimal formulation [Fe4S4]-(micro2-SCys)-[M((micro2-SCys)2Gly)Ni] with M = NiII, CuI, and ZnII at sites distal and proximal, respectively, to the iron-sulfur cluster. Bridges supported by representations of the distal nickel site were sought by reactions of the complexes [NiII(LH-S2N2)]2- and [NiII(LR-S2N2)], with 5-5-5 chelate ring patterns. Reaction products implicate the bridges Ni-(micro2-S)1,2-M in a variety of molecular structures, some with previously unknown connectivities of bridge atoms. The most frequently encountered bridge units are the nonplanar rhombs Ni(2-S)2M involving both sulfur atoms of a given complex. Those with M = NiII are biologically relevant inasmuch as the catalytic metal at the proximal site is nickel. The complex [Ni(L-655)]2-, containing the 6-5-5 ring pattern and coordination sphere of the distal nickel site, was prepared and structurally characterized. It was shown to sustain Ni2(micro2-S)2 rhombic interactions in the form of trinuclear [[Ni(L-655)]2Ni]2- and [[Ni(L-655)]Ni(R2PCH2CH2PR2)] (R = Et, Ph) in which the second NiII simulates the proximal site. Bridging interactions of NiII-S2N2 complexes are summarized, and geometrical features of Ni2(2-S)2 rhombs in these complexes, as dependent on ring patterns, are considered (LH-S2N2 = N,N'-ethylenebis(2-mercaptoisobutyramide)(4-); LR-S2N2 = trans-rac-N,N'-bis(2-mercapto-2-methylprop-1-yl)-1,2-cyclohexanediamine(2-); L-655 = N-(2-mercaptopropyl)-N'-(2'-mercaptoethyl)glycinamide(4-)).     

Fragmentation of certain substituted azadispiro(5.1.5.2)pentadec-9-ene and azadispiro(4.1.4.2)tridec-8-ene derivatives under electron ionization

A study of the electron ionization mass spectra of certain azadispiro(5.1.5.2)pentadec-9-ene-7,15-diones and azadispiro(4.1.4.2)tridec-8-ene-6,13-diones and their derivatives has revealed that these molecules undergo fragmentation primarily by two routes, viz. loss of CO and elimination of the substituent on the pyrrolidine nitrogen. Under positive ionization conditions loss of CO is the predominant process in the diones as it releases the ring strain, while in the 6- or 7-ols loss of the substituent on nitrogen is the favoured pathway. The further decomposition pathways of these primary fragments [M ? CO]⁺˙ and [M ? OR³]⁺ have been delineated with the help of high-resolution mass measurements, D₂O exchange and metastable spectra, These compounds give very simple negative ion spectra showing only [M ? OR³]^? and [NCO]^? ions except the N-hydroxy compounds which show [M ? H]^? ions as well.     

Phase retrieval in DSSI for relatively large deformation

Methods for phase retrieval in digital speckle shearing interferometry (DSSI) with relatively large deformation are proposed using a single wavelength illumination with windowed Fourier filtering (WFF) and two-wavelength simultaneous illumination with iterative sine-cosine average filtering (ISCAF). For relatively large deformation measurement, WFF technique has a higher noise suppression capability than ISCAF technique but requires careful selection of the processing parameters, while ISCAF is a simple filtering with less parameter setting. Both methods for phase retrieval are discussed. Experimental results show that both methods are capable of noise suppression in the phase retrieval for relatively large deformation.     

Measurement of surface figure of plane optical surfaces with polarization phase-shifting Fizeau interferometer

A Fizeau interferometer based set up for measurement of surface forms of plane optical surfaces has been discussed. Phase shifting interferometry has been applied using polarization phase shifter. A linearly polarized (632.8 nm) He–Ne laser has been used as the source. Light reflected from the object and the reference/master surfaces are made circularly polarized in opposite senses by means of two properly oriented quarter wave retardation plates placed at appropriate positions, one inside and other outside the interference cavity of the interferometer, and phase shifts are introduced between the object and the reference/master waves by varying angular orientation of a polarizer/analyzer. Final result is made free from any residual wave-front aberrations introduced by the (intra-cavity) wave plate by subtracting phase values obtained by PSI technique between a high optical quality master surface and the reference surface from that obtained for the test object surface with respect to the same reference surface for each point of the interference field. Results are shown for a plane surface.Advantages of the technique presented are linearity and high accuracy in phase stepping, no perturbation of the interference cavity during the phase shifting and possibility of real time or dynamic interferometry.     

A comparative study of phase-shifting algorithms in digital speckle pattern interferometry

Digital speckle pattern interferometry (DSPI) is a tool for making qualitative as well as quantitative measurements of deformation of objects. Phase-shifting algorithms in DSPI are useful for extracting quantitative deformation data from the system. Comparative studies of the different phase-shifting algorithms in DSPI for object deformation measurement are presented. Static and quasi-dynamic deformation of the object can be measured using these algorithms. Error compensating five-step phase-shifting method is used for the algorithms.     

MgCl(2).6PhCH2OH--a new molecular adduct as support material for Ziegler-Natta catalyst: synthesis, characterization and catalytic activity

Benzyl alcohol has been used to prepare a single phase MgCl(2).6BzOH molecular adduct as a support for an ethylene polymerization catalyst (Ziegler catalyst). The structural, spectroscopic and morphological aspects of the MgCl(2).6BzOH molecular adduct and the Ziegler catalyst have been thoroughly studied by various physicochemical characterization techniques. The presence of MgO(6) octahedrons due to the interaction of Mg(2+) with six -OH groups of the benzyl alcohol is confirmed from a Raman feature at 703 cm(-1), and structural studies. The supported catalyst activity has been evaluated for the ethylene polymerization reaction. The lower polymerization activity of the titanated Ziegler-Natta catalyst compared with a standard catalyst is attributed to the strong interaction of titanium chloride with the support and associated electronic factors.     

Azimuthal pion fluctuation in ultra relativistic nuclear collisions and centrality dependence—a study with chaos based complex network analysis

Various works on multiplicity fluctuation have investigated the dynamics of particle production process and eventually have tried to reveal a signature of phase transition in ultra-relativistic nuclear collisions. Analysis of fluctuations of spatial patterns has been conducted in terms of conventional approach. However, analysis with fractal dynamics on the scaling behavior of the void has not been explored yet. In this work we have attempted to analyze pion fluctuation in terms of the scaling behavior of the void probability distribution in azimuthal space in ultra-relativistic nuclear collisions in the light of complex networks. A radically different and rigorous method viz. Visibility Graph was applied on the data of ³²S-Ag/Br interaction at an incident energy of 200 GeV per nucleon. The analysis reveals strong scaling behavior of void probability distributions in azimuthal space and a strong centrality dependence.