Reactivity Of Pph3 Toward Ruiiruiiicl(O2car)4 - Syntheses, Molecular-Structures, And Spectroscopic And Electrochemical Properties Of Ruiiruiii(Oh2)Cl(Mecn)(O2car)4(Pph3)2 And Ruii2(Oh2)(Mecn)2(O2car)4(Pph3)2

By the reaction of Ru2Cl(O2CAr)4 (1) and PPh3 in MeCN-H2O the diruthenium(II,III) and diruthenium(II) compounds of the type Ru2(OH2)Cl(MeCN)(O2CAr)4(PPh3)2 (2) and Ru2(OH2)(MeCN)2(O2CAr)4(PPh3)2 (3) were prepared and characterized by analytical, spectral, and electrochemical data (Ar is an aryl group, C6H4-p-X; X = H, OMe, Me, Cl, NO2). The molecular structure of Ru2(OH2)Cl(MeCN)(O2CC6H4-p-OMe)4(PPh3)2 was determined by X-ray crystallography. Crystal data are as follows: triclinic, P1BAR, a = 13.538 (5) angstrom, b = 15.650 (4) angstrom, c = 18.287 (7) angstrom, alpha = 101.39 (3)-degrees, beta = 105.99 (4)-degrees, gamma = 97.94 (3)-degrees, V = 3574 angstrom 3, Z = 2. The molecule is asymmetric, and the two ruthenium centers are clearly distinguishable. The Ru(III)-Ru(II), Ru(III)-(mu-OH2), and Ru(II)-(mu-OH2) distances and the Ru-(mu-OH2)-Ru angle in [{Ru(III)Cl(eta-1-O2CC6H4-p-OMe)(PPh3)}(mu-OH2)(mu-O2CC6H4-p-OMe)2{Ru(II)(MeCN)(eta-1-O2CC6H4-p-OMe)(PPh3)}] are 3.604 (1), 2.127 (8), and 2.141 (10) angstrom and 115.2 (5)-degrees, respectively. The compounds are paramagnetic and exhibit axial EPR spectra in the polycrystalline form. An intervalence transfer (IT) transition is observed in the range 900-960 nm in chloroform in these class II type trapped mixed-valence species 2. Compound 2 displays metal-centered one-electron reduction and oxidation processes near -0.4 and +0.6 V (vs SCE), respectively in CH2Cl2-TBAP. Compound 2 is unstable in solution phase and disproportionates to (mu-aquo)diruthenium(II) and (mu-oxo)diruthenium(III) complexes. The mechanistic aspects of the core conversion are discussed. The molecular structure of a diruthenium(II) compound, Ru2(OH2)(MeCN)2(O2CC6H4-p-NO2)4(PPh3)2.1.5CH2Cl2, was obtained by X-ray crystallography. The compound crystallizes in the space group P2(1)/c with a = 23.472 (6) angstrom, b = 14.303 (3) angstrom, c = 23.256 (7) angstrom, beta = 101.69 (2)-degrees, V = 7645 angstrom 3, and Z = 4. The Ru(II)-Ru(II) and two Ru(II)-(mu-OH2) distances and the Ru(II)-(mu-OH2)-Ru(II) angle in [{(PPh3)-(MeCN)(eta-1-O2CC6H4-p-NO2)Ru}2(mu-OH2)(mu-O2CC6H4-p-NO2)2] are 3.712 (1), 2.173 (9), and 2.162 (9) angstrom and 117.8 (4)-degrees, respectively. In both diruthenium(II,III) and diruthenium(II) compounds, each metal center has three facial ligands of varying pi-acidity and the aquo bridges are strongly hydrogen bonded with the eta-1-carboxylato facial ligands. The diruthenium(II) compounds are diamagnetic and exhibit characteristic H-1 NMR spectra in CDCl3. These compounds display two metal-centered one-electron oxidations near +0.3 and +1.0 V (vs SCE) in CH2Cl2-TBAP. The overall reaction between 1 and PPh3 in MeCN-H2O through the intermediacy of 2 is of the disproportionation type. The significant role of facial as well as bridging ligands in stabilizing the core structures is observed from electrochemical studies.

Dopamine receptors in human foetal brains:Characterization, regulation and ontogeny of [3H]spiperone binding sites in striatum

Eighteen corpora striata from normal human foetal brains ranging in gestational age from 16 to 40 weeks and five from post natal brains ranging from 23 days to 42 years were analysed for the ontogeny of dopamine receptors using [3H]spiperone as the ligand and 10 mM dopamine hydrochloride was used in blanks. Spiperone binding sites were characterized in a 40-week-old foetal brain to be dopamine receptors by the following criteria: (1) It was localized in a crude mitochondrial pellet that included synaptosomes; (2) binding was saturable at 0.8 nM concentration; (3) dopaminergic antagonists spiperone, haloperidol, pimozide, trifluperazine and chlorpromazine competed for the binding with IC50 values in the range of 0.3–14 nM while agonists—apomorphine and dopamine gave IC50 values of 2.5 and 10 μM, respectively suggesting a D2 type receptor.Epinephrine and norepinephrine inhibited the binding much less efficiently while mianserin at 10 μM and serotonin at 1 mM concentration did not inhibit the binding. Bimolecular association and dissociation rate constants for the reversible binding were 5.7 × 108 M−1 min−1 and 5.0 × 10−2 min−1, respectively. Equilibrium dissociation constant was 87 pM and the KD obtained by saturation binding was 73 pM.During the foetal age 16 to 40 weeks, the receptor concentration remained in the range of 38–60 fmol/mg protein or 570–1080 fmol/g striatum but it increased two-fold postnatally reaching a maximum at 5 years Significantly, at lower foetal ages (16–24 weeks) the [3H]spiperone binding sites exhibited a heterogeneity with a high (KD, 13–85 pM) and a low (KD, 1.2–4.6 nM) affinity component, the former accounting for 13–24% of the total binding sites. This heterogeneity persisted even when sulpiride was used as a displacer. The number of high affinity sites increased from 16 weeks to 24 weeks and after 28 weeks of gestation, all the binding sites showed only a single high affinity.GTP decreased the agonist affinity as observed by dopamine competition of [3H]spiperone binding in 20-week-old foetal striata and at all subsequent ages. GTP increased IC50 values of dopamine 2 to 4.5 fold and Hill coefficients were also increased becoming closer to one suggesting that the dopamine receptor was susceptible to regulation from foetal life onwards.

Synthesis, structure and ionic conductivity in scheelite type Li(0.5)Ce(0.5-x)Ln(x)MoO(4) (x=0 and 0.25, Ln = Pr, Sm)

Scheelite type solid electrolytes, Li(0.5)Ce(0.5-x)Ln(x)MoO(4) (x = 0 and 0.25, Ln = Pr, Sm) have been synthesized using a solid state method. Their structure and ionic conductivity (a) were obtained by single crystal X-ray diffraction and ac-impedance spectroscopy, respectively. X-ray diffraction studies reveal a space group of I4(1)/a for Li(0.5)Ce(0.5-x)Ln(x)MoO(4) (x = 0 and 0.25, Ln = Pr, Sm) scheelite compounds. The unsubstituted Li0.5Ce0.5MoO4 showed lithium ion conductivity similar to 10(-5)-10(-3) Omega(-1)cm(-1) in the temperature range of 300-700 degrees C (sigma = 2.5 x 10(-3) Omega(-1) cm(-1) at 700 degrees C). The substituted compounds show lower conductivity compared to the unsubstituted compound, with the magnitude of ionic conductivity being two (in the high temperature regime) to one order (in the low temperature regime) lower than the unsubstituted compound. Since these scheelite type structures show significant conductivity, the series of compounds could serve in high temperature lithium battery operations.

Constructions of 2D-Metallamacrocycles Using Half-Sandwich Ru-2(II) Precursors: Synthesis, Molecular Structures, and Self-Selection for a Single Linkage Isomer

Coordination-driven self-assembly of oxalato-bridged half-sandwich p-cymene ruthenium complex Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)] (O3SCF3)(2) (1a) with several ditopic donors (L-a-L-d) in methanol affords a series of bi- and tetranuclear metallamacrocycles (2a and 3-5). Similarly, the combination of 2,5-dihydroxy-1,4-benzoquinonato (dhbq)-bridged binuclear complex Ru-2(mu-eta(4)-C6H2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1b) with a flexible bidentate amide linker (L-a) in 1:1 molar ratio gave the corresponding tetranuclear complex 2b. All the macrocycles were isolated as their triflate salts in high yields and were fully characterized by various spectroscopic techniques. Finally, the molecular structures of all the assemblies were determined unambiguously by single-crystal X-diffraction analysis. Interestingly, the combination of acceptor 1a or 1b with an unsymmetrical linear ditopic donor L-a results in a self-sorted linkage isomeric (head-to-tail) macrocycle (2a or 2b) despite the possibility of formation of two different isomeric macrocycles (head-to-head or head-to-tail) due to different connectivity of the donor. Molecular structures of the complexes 2a and 2b showed tetranuclear rectangular geometry with dimensions of 5.51 angstrom x 13.29 angstrom for 2a and 7.91 angstrom x 13.46 angstrom for 2b. In both cases, two binuclear Ru-2(II) building blocks are connected by a mu-N-(4-pyridyl)isonicotinamide donor in a head-to-tail fashion. Surprisingly, the macrocycle 2a loses one counteranion and cocrystallizes with monodeprotonated 1,3,5-trihydroxybenzene via strong intermolecular pi-pi stacking and hydrogen bonding. The tweezer complex 3 showed strong fluorescence in solution, and it showed fluorescence sensing toward nitroaromatic compounds. A fluorescence study demonstrated a marked quenching of the initial fluorescence intensity of the macrocycle 3 upon gradual addition of trinitrotoluene and exhibits significant fluorescence quenching response only for nitroaromatic compounds compared to various other aromatic compounds tested.

Structure of N-nitroso-r-2,c-7-diphenylhexahydro-1,4-diazepin-5-one

C17H17N3O2, M(r) = 295.34, orthorhombic, P2(1)2(1)2(1), a = 7.659 (1), b = 12.741 (1), c = 15.095 (1) angstrom, V = 1473.19 (2) angstrom 3, Z = 4, D(m) = 1.33, D(x) = 1.32 Mg m-3, lambda(Cu K-alpha) = 1.5418 angstrom, mu = 0.68 mm-1, F(000) = 624, T = 295 K, R = 0.031 for 1549 unique observed reflections with I > 2.5-sigma(I). The seven-membered heterocyclic ring adopts a boat conformation flattened at the nitroso end of the ring. The substituent phenyl rings occupy pseudo-axial positions and the nitroso group is coplanar with the C(2), N(1), C(7) plane of the central ring. The crystal structure is stabilized by intermolecular N-H...O and weak C-H...O hydrogen bonds.

Synthesis Based on Cyclohexadienes. 5. A New Approach to the Synthesis of a-Ring Aromatic Steroids - a Formal Total Synthesis of (+/-)-Estrone

A new strategy for the construction of A-ring aromatic steroids which resulted in the formal total synthesis of estrone is described. Thus reaction of the adduct (9), obtained from 1-methoxy-4-methylcyclohexa-1,4-diene and acrolein, with 3-(m-methoxyphenyl)propylmagnesium bromide followed by oxidation afforded the bicyclo[2.2.2]octene derivative (14). Acid-catalysed rearrangement of (14) followed by an intramolecular Michael addition resulted in the cis tetraenone (18) which was dehydrogenated with palladium chloride to the pentaenone (22). Li/NH3 reduction of (22) gave 3-methoxy-D-homoestra-1,3,5(10)-trien-16-one (31) which has been converted into the methyl ether (37) of marrianolic acid, and its methyl ester (38).

Diphenylantimony(V) oxo/chloro carboxylates and phosphinates: crystal structures of {SbPh2Cl[O2P(C6H11)2]}2O and [SbPh2(O2CPh)2]2O

Reaction of SbPh(2)Cl(3) (1 mol) with the silver salt of dicyclohexylphosphinic acid (2 mol) afforded {SbPh(2)Cl[O2P(C6H11)(2)]}O-2 1, a similar reaction with AgO2P(C8H15)(2) gave a product formulated as {SbPh(2)Cl[O2P(C8H15)(2)]}O-2 2. Similar reactions with silver carboxylates (1:3 stoichiometry) led to the crystalline derivatives [SbPh(2)(O(2)CR)(2)]O-2 (R = Ph 3, CHPh(2) 4, 2,4,6-Me(3)C(6)H(2) 5, 2-MeC(6)H(4) 6 or 4-MeC(6)H(4) 7), whereas the 1:2 reaction afforded crystalline SbPh(2)Cl(O(2)CR)(2) (R = Ph 8, 2-MeC(6)H(4) 9 or 4-MeC(6)H(4) 10). Interconversion of the previously known compounds [SbPh(2)(O(2)CMe)(2)]O and Sb(4)Ph(8)O(6) . 3MeCO(2)H was achieved and established by H-1 NMR spectroscopy. Compounds 1 and 3 were further characterized by X-ray diffraction; the antimony in 1 is six-co-ordinated with bridging phosphinates whereas in 3 it is seven-co-ordinated with chelating benzoates. Short Sb-O (oxo) distances (1.923 Angstrom) and near linearity at the bridging ox

Zn(II), Cd(II) and Hg(II) complexes with 1-(p-methoxybenzyl)-2-(p-methoxyphenyl)benzimidazole: Syntheses, structures and luminescence

Five coordination compounds Zn(mbmpbi)(2)Cl-2 (1), Zn(mbmpbi)(2)Br-2 (2), Cd(mbmpbi)(2)Cl-2 (3), Hg(mbmpbi)(2)Cl-2 (4) and Hg(mbmpbi)(2)Br-2 (5) were synthesized by the reaction of 1-(p-methoxybenzyl)-2-(p-methoxyphenyl)benzimidazole (mbmpbi) with the corresponding metal halides. The complexes have been characterized by elemental analysis, conductance measurements, FT-IR, H-1 NMR and photoluminescence spectral studies. The ligand mbmpbi exhibits the N-benzimidazole coordination. The structures of 3-5 have been determined by single crystal X-ray diffraction. These three complexes are isostructural, crystallizing in the monoclinic system. P2/n space group with a distorted tetrahedral geometry around the metal ion. Zn(II) and Cd(II) complexes show strong blue emission in solid state at room temperature. (C) 2011 Elsevier Ltd. All rights reserved.

Reactivity of some tetra substituted furans and thiophenes towards BF3-Et(2)O catalysed Diels-Alder reaction

Some tetra substituted furans and thiophenes were reacted with methyl acrylate under BF3-etherate catalysed Diels-Alder conditions. While the derivatives of furan underwent Diels-Alder reaction in a facile manner, an observation of 2,5-dimethyl-3,4-dianisylthiophene undergoing Diels-Alder reaction with methyl acrylate is remarkable. (C) 1997, Elsevier Science Ltd.

Oxidative addition of tetrachloro-1,2-benzoquinone to lambda(3)-cyclotriphosphazanes. An unusual ring contraction-rearrangement

The lambda(3)-cyclotriphosphazanes, [EtNP(OR)](3) [R = 2,6-Me2C6H3 (1), 4-BrC6H4 (2), or CH2CF3(3)], on treatment with tetrachloro-1,2-benzoquinone (TCB) give the lambda(5)-cyclodiphosphazanes, [EtNP(O2C6Cl4)(OR)][EtNP(O2C6Cl4){N(Et)P(OR)(2)}] (5-7) by an unusual ring contraction-rearrangement. The reaction of the mixed substituent lambda(3)-cyclotriphosphazane, [(EtN)(3)P-3(OR)(2)(OR')] [R = 2,6-Me2C6H3, R' = 4-BrC6H4] (4), with TCB gives the lambda(5)-cyclodiphosphazane, [EtNP(O2C6Cl4)(OR')][EtNP(O2C6Cl4){N(Et)P(OR)(2)}] (8), in which 4-bromophenoxide resides on one of the ring phosphorus atoms. The lambda(3)-bicyclic tetraphosphapentazane, (EtN)(5)P-4(OPh)(2), on treatment with TCB undergoes a double ring contraction-rearrangement to give the lambda(5)-cyclodiphosphazane, (EtN)[(EtN)(2)P-2(O2C6Cl4)(2)(OPh)](2) (9). Variable-temperature and high-field P-31 NMR studies indicate the presence of more than one isomer in solution for the rearranged products 5-9. The solid state structure of 8 reveals a trans arrangement of the substituents with respect to the P2N2 ring in contrast to the gauche arrangement observed for 5.

Thermodynamic studies on NdFeO3(s)

The enthalpy increments and the standard molar Gibbs energy of formation of NdFeO3(s) have been measured using a hightemperature Calvet microcalorimeter and a solid oxide galvanic cell, respectively. A lambda-type transition, related to magnetic order-disorder transformation (antiferromagnetic to paramagnetic), is apparent from the heat capacity data at similar to 687 K. Enthalpy increments, except in the vicinity of transition, can be represented by a polynomial expression: {Hdegrees(m)(T)-Hdegrees(m) (298.15 K)} /J(.)mol(-1) (+/- 0.7%)=-53625.6+146.0(T/K) +1.150 X 10(-4)(T/K)(2) +3.007 x 10(6)(T/K)(-1); (298.15 less than or equal to T/K less than or equal to 1000). The heat capacity, the first differential of {Hdegrees(m)(T)-Hdegrees(m)(298.15 K)}with respect to temperature, is given by Cdegrees(pm)/J(.)K(-1.)mol(-1)=146.0+ 2.30x10(-4) (T/K) - 3.007 X 10(6)(T/K)(-2). The reversible emf's of the cell, (-) Pt/{NdFeO3(s) +Nd2O3(s)+Fe(s)}//YDT/CSZ// Fe(s)+'FeO'(s)}/Pt(+), were measured in the temperature range from 1004 to 1208 K. It can be represented within experimental error by a linear equation: E/V=(0.1418 +/- 0.0003)-(3.890 +/- 0.023) x 10(-5)(T/K). The Gibbs energy of formation of solid NdFeO, calculated by the least-squares regression analysis of the data obtained in the present study, and data for Fe0.95O and Nd2O3 from the literature, is given by Delta(f)Gdegrees(m)(NdFeO3 s)/kJ (.) mol(-1)( +/- 2.0)=1345.9+0.2542(T/K); (1000 less than or equal to T/K less than or equal to 1650). The error in Delta(f)Gdegrees(m)(NdFeO3, s, T) includes the standard deviation in emf and the uncertainty in the data taken from the literature. Values of Delta(f)Hdegrees(m)(NdFeO3, s, 298.15 K) and Sdegrees(m) (NdFeO3 s, 298.15 K) calculated by the second law method are - 1362.5 (+/-6) kJ (.) mol(-1) and 123.9 (+/-2.5) J (.) K-1 (.) mol(-1), respectively. Based on the thermodynamic information, an oxygen potential diagram for the system Nd-Fe-O was developed at 1350 K. (C) 2002 Elsevier Science (USA).

Monodisperse sub-10 nm gold nanoparticles by reversing the order of addition in Turkevich method - The role of chloroauric acid

The Turkevich method for synthesizing gold nanoparticles, using sodium citrate as the reducing agent, is renowned for its ability to produce biocompatible colloids with mean size >10 nm. Here we show that monodisperse gold nanoparticles in the 5-10 nm size range can be synthesized by simply reversing the order of addition of reactants, i.e. adding chloroauric acid to citrate solution. Kinetic studies and electron microscopic characterization revealed that the reactivity of chloroauric acid, initial molar ratio of citrate to chloroauric acid (MR), and reaction mixture pH play an important role in producing monodisperse gold nanoparticles. Reversing the order of addition also enhanced the stabilization of nanoparticles at high MR values. Remarkably, the system exhibits a `memory' of the order of addition, even when the timescale of mixing is much shorter than the timescale of synthesis. (C) 2011 Elsevier Inc. All rights reserved.

The effect of host glass on optical absorption and fluorescence of Nd3+ in xNa(2)O-(30-x)K2O-70B(2)O(3) glasses

The effect of host glass composition on the optical absorption and fluorescence spectra of Nd3+ has been studied in mixed alkali borate glasses of the type xNa(2)O-(30-x)K2O-69.5B(2)O(3)-0.5Nd(2)O(3) (X = 5,10,15,20 and 25). Various spectroscopic parameters such as Racah (E-1, E-2 and E-3), spin-orbit (xi(4f)) and configuration interaction (alpha, beta) parameters have been calculated. The Judd-Ofelt intensity parameters (Omega(lambda)) have been calculated and the radiative transition probabilities (A(rad)), radiative lifetimes (tau(r)), branching ratios (beta) and integrated absorption cross sections (Sigma) have been obtained for certain excited states of the Nd3+, ion and are discussed with respect to x. From the fluorescence spectra, the effective fluorescence line widths (Deltalambda(eff)) and stimulated emission cross sections (sigma(p)) have been obtained for the three transitions F-4(3/2) --> I-4(9/2), F-4(3/2) --> I-4(11/2) and F-4(3/2) --> I-4(13/2) of Nd3+. The stimulated emission cross section (sigma(p)) values are found to be in the range (2.0-4.8) x 10(-2)0 cm(2) and they are large enough to indicate that the mixed alkali borate glasses could be potential laser host materials.

Nature of Electronic States in Atomically Thin MoS(2) Field-Effect Transistors

We present low-temperature electrical transport experiments in five field-effect transistor devices consisting of monolayer, bilayer, and trilayer MoS(2) films, mechanically exfoliated onto Si/SiO(2) substrate. Our experiments reveal that the electronic states In all films are localized well up to room temperature over the experimentally accessible range of gate voltage. This manifests in two-dimensional (2D) variable range hopping (VRH) at high temperatures, while below similar to 30 K, the conductivity displays oscillatory structures In gate voltage arising from resonant tunneling at the localized sites. From the correlation energy (T(0)) of VRH and gate voltage dependence of conductivity, we suggest that Coulomb potential from trapped charges In the substrate is the dominant source of disorder in MoS(2) field-effect devices, which leads to carrier localization, as well.

Synthesis and Antileukemic Activity of Novel 2-(4-(2,4-dimethoxybenzoyl)phenoxy)-1-(4-(3-(piperidin-4-yl)propyl)piper idin-1-yl)ethanone Derivatives

A series of novel 2-(4-(2,4-dimethoxybenzoyl)phenoxy)-1-(4-(3-(piperidin-4-yl)propyl) piperidin-1-yl)ethanone derivatives 9(ae) and 10(ag) were synthesized and characterized by 1H NMR, IR, mass spectral, and elemental analysis. These novel compounds were evaluated for their antileukemic activity against two human leukemic cell lines (K562 and CEM) by using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromide assay. Some of the tested compounds showed good antiproliferative activity with IC50 values ranging from 1.6 to 8.0 mu m. Compound 9c, 9e, and 10f with an electron-withdrawing halogen substituent at the para position on the phenyl ring showed excellent in vitro potency against tested human leukemia cells (K562 and CEM).