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21.
Rama Acharyya Shie-Ming Peng Ren-Zhang Wang Samaresh Bhattacharya 《Journal of organometallic chemistry》2005,690(17):3908-3917
Reaction of 2-(2′,6′-dimethylphenylazo)-4-methylphenol with [Ir(PPh3)3Cl] in refluxing ethanol in the presence of a base (NEt3) affords an organoiridium complex 5, where the 2-(2′,6′-dimethylphenylazo)-4-methylphenol is coordinated to iridium, via C-H activation of a methyl group, as a dianionic tridentate C,N,O-donor. Two triphenylphosphines and a hydride are also coordinated to the metal center. A similar reaction carried out in toluene affords complex 5 along with a similar complex 7, where a chloride is coordinated to iridium instead of the hydride. Reaction of 2-(2′-methylphenylazo)-4-methylphenol with [Ir(PPh3)3Cl] in refluxing ethanol in the presence of a base (NEt3) affords an organoiridium complex 12, where the 2-(2′-methylphenylazo)-4-methylphenol is coordinated to iridium, via C-H activation at the ortho position of the phenyl group in the 2′-methylphenylazo fragment, as a dianionic tridentate C,N,O-donor. Two triphenylphosphines and a hydride are also coordinated to the metal center. A similar reaction carried out in toluene affords a complex 12 along with a similar complex 13, where a chloride is coordinated to iridium instead of the hydride. Structures of complexes 5, 12 and 13 have been determined by X-ray crystallography. In all these complexes, the two triphenylphosphines are trans. All these complexes show intense MLCT transitions in the visible region. Cyclic voltammetry on all the complexes shows an Ir(III)-Ir(IV) oxidation within 0.60-0.73 V vs. SCE, followed by an oxidation of the coordinated 2-(arylazo)phenolate ligand within 1.08-1.39 V vs. SCE. A reduction of the coordinated 2-(arylazo)phenolate ligand is observed within −1.10 to −1.26 V vs. SCE. 相似文献
22.
The phase transitions of nearest-neighbour interacting Ising models on self-avoiding walk (SAW) chains on square and triangular lattices have been studied using Monte Carlo technique. To estimate the transition temperature (T
c) bounds, the average number of nearest-neighbours (Z
eff) of spins on SAWs have been determined using the computer simulation results, and the percolation thresholds (p
c) for site dilution on SAWs have been determined using Monte Carlo methods. We find, for SAWs on square and triangular lattices respectively,Z
eff=2.330 and 3.005 (which compare very well with our previous theoretically estimated values) andp
c=0.022±0.003 and 0.045±0.005. When put in Bethe-Peierls approximations, the above values ofZ
eff givekT
c/J<1.06 and 1.65 for Ising models on SAWs on square and triangular lattices respectively, while, using the semi-empirical relation connecting the Ising modelT
c's andp
c's for the same lattices, we findkT
c/J0.57 and 0.78 for the respective models. Using the computer simulation results for the shortest connecting path lengths in SAWs on both kinds of lattices, and integrating the spin correlations on them, we find the susceptibility exponent =1.024±0.007, for the model on SAWs on two dimensional lattices. 相似文献
23.
Tara Chandra Gupta Abani K. Bhattacharya 《Fresenius' Journal of Analytical Chemistry》1960,172(6):428-430
Summary The only method recommended for the direct estimation of ferric iron in presence of HCl is to reduce the ferric iron to ferrous iron and then to titrate against KMnO4 solution by adding Reinhardt-Zimmermann reagent (MnSO4 + H2SO4 + H3PO4). The solubility of the phosphato complexes of ferric chloride and phosphoric acid is much reduced by adding a nonaqueous solvent, ethyl alcohol or acetone. This property has been availed of to find out a method of estimating ferric iron directly against standard solution of phosphoric acid in aqueous-nonaqueous medium using K4Fe(CN)6 or cupferron as external indicators. A slight discrepancy at the end point, however, exists in the direct titration but it can be removed by applying a correction factor determined from the estimated results. 相似文献
24.
In aqueous solution ruthenium trichloride reacted with picolinic acid (Hpic) in the presence of a base to afford [Ru(pic)3]. In solution it shows intense ligand-to-metal charge transfer transitions near 310 and 370 nm, together with a low-intensity absorption near 2000 nm. [Ru(pic)3] is one-electron paramagnetic and shows a rhombic ESR spectrum in 1:1 dimethylsulphoxide-methanol solution at 77 K. The distortions from octahedral symmetry have been calculated by ESR data analysis. The axial distortion is larger than the rhombic one. In acetonitrile solution it shows a reversible ruthenium(III)-ruthenium(II) reduction at −0.09 V vs. SCE and a reversible ruthenium(III)-ruthenium(IV) oxidation at 1.52 V vs. SCE. Chemical or electrochemical reduction of [RuIII(pic)3] gives [RuII(pic)3]−, which in solution shows intense MLCT transitions near 360, 410 and 490 nm, and is converted back to [Ru(pic)3] by exposure to air. Reaction of [Ru(pic)3] with 8-quinolinol (HQ) in dimethylsulphoxide solution affords [RuQ3]. [Ru(bpy)(pic)2] (bpy = 2,2′-bipyridine) has been prepared by the reaction of Hpic with [Ru(bpy)(acac)2]Cl (acac = acetylacetonate ion) in ethyleneglycol. It is diamagnetic and in solution shows intense MLCT transitions near 370, 410 and 530 nm. In acetonitrile solution it shows a reversible ruthenium(II)-ruthernium(III) oxidation at 0.44 V vs. SCE and a reversible one-electron reduction of bpy at − 1.64V vs. SCE. 相似文献
25.
The structural features of quinone ligands are diagnostic of charge. The o-benzoquinone, radical semiquinonate, and catecholate electronic forms have C-O bond lengths and a pattern of ring C-C bond lengths that point to a specific mode of coordination. This correlation between ligand charge and structure has been extended to iminoquinone and iminothioquinone ligands, giving a charge-localized view of electronic structure for complexes of redox-active metal ions. The radical semiquinonate form of these ligands has been found to be a surprisingly common mode of coordination; however, the paramagnetic character of the radical ligand is often obscured in complexes containing paramagnetic metal ions. In this report, diamagnetic iminosemiquinonate (isq) and iminothiosemiquinonate (itsq) complexes of ls-d(5) Ru(III) with related complexes of osmium are reported. With osmium, the Os(IV)-amidophenolate (ap) redox isomer is formed. Electrochemical and spectral properties are described for Ru(PPh(3))(2)(isq)Cl(2), Ru(PPh(3))(2)(itsq)Cl(2), Os(PPh(3))(2)(ap)Br(2), Os(PPh(3))(2)(atp)Br(2), and Os(PPh(3))(2)(ap)H(2). Crystallographic characterization of Ru(PPh(3))(2)(isq)Cl(2), Ru(PPh(3))(2)(itsq)Cl(2), and Os(PPh(3))(2)(ap)H(2) was used to assign charge distributions. 相似文献
26.
We have studied the effect of shape of an amphiphilic molecule on micellization properties by carrying out stochastic molecular dynamics simulation on a bead-spring model of amphiphiles for several sizes of hydrophilic head group with a fixed hydrophobic tail length. Our studies show that the effect of geometry of an amphiphile on shape and cluster distribution of micelles is significant. We find the critical micelle concentration increases with the increasing size of the hydrophilic head. We demonstrate that the onset of micellization is accompanied by (i) a peak in the specific heat as found earlier in the simulation studies of lattice models, and (ii) a peak in the characteristic relaxation time of the cluster autocorrelation function. Amphiphiles with larger hydrophilic head form smaller micelles with sharper cluster distribution. Our studies are relevant to the controlled synthesis of nanostructures of desired shapes and sizes using self-assembling properties of amphiphiles. 相似文献
27.
Gupta P Das A Basuli F Castineiras A Sheldrick WS Mayer-Figge H Bhattacharya S 《Inorganic chemistry》2005,44(6):2081-2088
Reaction of chloranilic acid (H2ca) with [Os(bpy)2 Br2] (bpy = 2,2'-bipyridine) affords a dinuclear complex of type [{Os(bpy)2}2 (ca)]2+, isolated as the perchlorate salt. A similar reaction of H2ca with [Os(PPh3)2 (pap)Br2] (pap = 2-(phenylazo)pyridine) affords a dinuclear complex of type [{Os(PPh3)2 (pap)}2 (ca)]2+ (isolated as the perchlorate salt) and a mononuclear complex of type [Os(PPh3)2 (pap)(ca)]. Reaction of H2ca with [Os(PPh3)2(CO)2(HCOO)2] gives a dinuclear complex of type [{Os(PPh3)2(CO)2}2 (r-ca)], where r-ca is the two electron reduced form of the chloranilate ligand. The structures of the [{Os(PPh3)2 (pap)}2 (ca)](ClO4)2, [Os(PPh3)2 (pap)(ca)], and [{Os(PPh3)2(CO)2}2 (r-ca)] complexes have been determined by X-ray crystallography. In the [{Os(bpy)2}2 (ca)]2+ and [{Os(PPh3)2 (pap)}2 (ca)]2+ complexes, the chloranilate dianion is serving as a tetradentate bridging ligand. In the [Os(PPh3)2 (pap)(ca)] complex, the chloranilate dianion is serving as a bidentate chelating ligand. In the [{Os(PPh3)2(CO)2}2 (r-ca)] complex, the reduced form of the chloranilate ligand (r-ca(4-)) is serving as a tetradentate bridging ligand. All the four complexes are diamagnetic and show intense metal-to-ligand charge-transfer transitions in the visible region. The [Os(PPh3)2 (pap)(ca)] complex shows an Os(II)-Os(III) oxidation, followed by an Os(III)-Os(IV) oxidation on the positive side of a standard calomel electrode. The three dinuclear complexes show two successive oxidations on the positive side of SCE. The mixed-valent Os(II)-Os(III) species have been generated in the case of the two chloranilate-bridged complexes by coulometric oxidation of the homovalent Os(II)-Os(II) species. The mixed-valent Os(II)-Os(III) species show intense intervalence charge-transfer transitions in the near-IR region. 相似文献
28.
29.
On the functional central limit theorem and the law of the iterated logarithm for Markov processes 总被引:2,自引:0,他引:2
R. N. Bhattacharya 《Probability Theory and Related Fields》1982,60(2):185-201
Summary Let X
tt0 be an ergodic stationary Markov process on a state space S. If  is its infinitesimal generator on L
2(S, dm), where m is the invariant probability measure, then it is shown that for all f in the range of
} } 0)$$
" align="middle" border="0">
converges in distribution to the Wiener measure with zero drift and variance parameter
2 =–2f, g=–2Âg, g where g is some element in the domain of  such that Âg=f (Theorem 2.1). Positivity of
2 is proved for nonconstant f under fairly general conditions, and the range of  is shown to be dense in 1. A functional law of the iterated logarithm is proved when the (2+)th moment of f in the range of  is finite for some >0 (Theorem 2.7(a)). Under the additional condition of convergence in norm of the transition probability p(t, x, d y) to m(dy) as t , for each x, the above results hold when the process starts away from equilibrium (Theorems 2.6, 2.7 (b)). Applications to diffusions are discussed in some detail.This research was partially supported by NSF Grants MCS 79-03004, CME 8004499 相似文献
30.
Asish K Bhattacharya Mahesh PalDharam C Jain Bhawani S JoshiRaja Roy Urszula RychlewskaRam P Sharma 《Tetrahedron》2003,59(16):2871-2876
Absolute stereochemistry of dihydroarteannuin B 5 obtained by the reduction of arteannuin B 3 with Ni2B, NaBH4 or CdCl2-Mg-MeOH-H2O has been established by 2D NMR and single crystal X-ray diffraction studies. Some experiments aimed at the synthesis of dihydrodeoxyarteannuin B [C-4, 5 double bond isomer of 11] are also discussed. 相似文献