Application of the Ru(bipy)2(dpp)2+ / C2O4 2− electrochemiluminescence reaction to the determination of phenol

The electrochemiluminescence (ECL) of the ruthenium di(2,2′-bipyridine)- (4,7-diphenyl-1,10-phenanthroline) complex (Ru-bipy-dpp) produced on a glassy carbon electrode was studied by cyclic voltammetry. The anodic oxidation of Ru-bipy-dpp produces ECL in the presence of oxalate in oxygen-free aqueous solutions. Threefold ECL efficiencies were obtained for Ru-bipy-dpp relative to Ru(bipy)₃ as a standard. The ECL of Ru-bipy-dpp is quenched by both oxygen and phenol. The luminescence intensity was proportional to the concentration of phenol in the range of 5–100 μM. At a phenol concentration of 100 μM, the ECL of Ru-bipy-dpp peaking at 597 nm was completely quenched. Correspondence: Dan Xiao, College of Chemistry and Chemical Engineering, Sichuan University, Chengdu 610065, P.R. China     

Application of the ABEEM/MM model in studying the properties of the water clusters(H_2O)_n(n=7-10)

ABEEM/MM model has been applied to compute the various properties characterizing water clusters(H2O) n(n = 7-10) ,such as optimized geometries,the hydrogen bonds number,cluster interaction en-ergies,stabilities,ABEEM charge distributions,dipole moments,structural parameters,and so on,and to describe the transition reflected by the hexamer region from two-dimensional(from dimer to pen-tamer) to three-dimensional structures(for clusters larger than the hexamer) .     

Oxidative addition of 2,2′-dithiosalicylic acid to the cluster [Os3(CO)10)(CH3CN)2]

The reaction of 2,2'-dithiosalicylic acid with two equivalents of [Os₃(CO)₁₀ (CH₃CN)] in THF at –78°C yields yellow crystals of [{Os₃(CO)₁₀(-H)}₂ (O₂CC₆H₄S)₂] 1 in moderate yield. Hydrogenetaion of 1 in refluxing CHCl₃ affords [Os₃(CO)₁(-H)(O₂CC₆H₅)] 2 in good yield. Structures of 1 and 2 have been established by single crystal X-ray structure analysis.     

Dependence of the chemical properties of macrocyclic [Ni(II)(2)L(μ-O(2)CR)](+) complexes on the basicity of the carboxylato coligands (L(2-) = macrocyclic N(6)S(2) ligand)

The dependence of the properties of mixed ligand [Ni(II)(2)L(μ-O(2)CR)](+) complexes (where L(2-) represents a 24-membered macrocyclic hexaamine-dithiophenolato ligand) on the basicity of the carboxylato coligands has been examined. For this purpose 19 different [Ni(II)(2)L(μ-O(2)CR)](+) complexes (2-20) incorporating carboxylates with pK(b) values in the range 9 to 14 have been prepared by the reaction of [Ni(II)(2)L(μ-Cl)](+) (1) and the respective sodium or triethylammonium carboxylates. The resulting carboxylato complexes, isolated as ClO(4)(-) or BPh(4)(-) salts, have been fully characterized by elemental analyses, IR, UV/vis spectroscopy, and X-ray crystallography. The possibility of accessing the [Ni(II)(2)L(μ-O(2)CR)](+) complexes by carboxylate exchange reactions has also been examined. The main findings are as follows: (i) Substitution reactions between 1 and NaO(2)CR are not affected by the basicity or the steric hindrance of the carboxylate. (ii) Complexes 2-20 form an isostructural series of bisoctahedral [Ni(II)(2)L(μ-O(2)CR)](+) compounds with a N(3)Ni(μ-SR)(2)(μ-O(2)CR)NiN(3) core. (iii) They are readily identified by their ν(as)(CO) and ν(s)(CO) stretching vibration bands in the ranges 1684-1576 cm(-1) and 1428-1348 cm(-1), respectively. (iv) The spin-allowed (3)A(2g) → (3)T(2g) (ν(1)) transition of the NiOS(2)N(3) chromophore is steadily red-shifted by about 7.5 nm per pK(b) unit with increasing pK(b) of the carboxylate ion. (v) The less basic the carboxylate ion, the more stable the complex. The stability difference across the series, estimated from the difference of the individual ligand field stabilization energies (LFSE), amounts to about 4.2 kJ/mol [Δ(LFSE)(2,18)]. (vi) The "second-sphere stabilization" of the nickel complexes is not reflected in the electronic absorption spectra, as these forces are aligned perpendicularly to the Ni-O bonds. (vii) Coordination of a basic carboxylate donor to the [Ni(II)(2)L](2+) fragment weakens its Ni-N and Ni-S bonds. This bond weakening is reflected in small but significant bond length changes. (viii) The [Ni(II)(2)L(μ-O(2)CR)](+) complexes are relatively inert to carboxylate exchange reactions, except for the formato complex [Ni(II)(2)L(μ-O(2)CH)](+) (8), which reacts with both more and less basic carboxylato ligands.     

Electrochemical oxidative addition of chloride to Rh2(μ-dppm)2(CO)2Cl2

The electrochemical oxidation of trans-Rh₂(μ-dppm)₂(CO)₂Cl₂ (dppm = bis (diphenylphosphino)methane) in the presence of chloride has afforded the new dirhodium(II) unsymmetrical complex Rh₂(μ-dppm)₂(μ-Cl)(CO)Cl₃ which is readily converted to the complex [Rh₂(μ-dppm)₂(μ-Co)(μ-Cl)Cl₂]PF₆. This species has been shown to undergo addition reactions with chloride to regenerate [Rh₂(μ-dppm)₂(μ-Cl)Cl₃(CO)], and with carbon monoxide and t-butylisocyanide to give the additional new dirhodium(II) complexes [Rh₂(μ-dppm)₂(μ-Cl)Cl₂(CO)₂]PF₆ and [Rh₂(μ-dppm)₂(μ-Cl)(CNC(CH₃)₃)₂Cl₂]PF₆, respectively. During prolonged exposure to carbon monoxide [Rh₂(μ-dppm)₂(μ-Co)(μ-Cl)Cl₂]PF₆ undergoes reduction with the loss of chloride to give [Rh₂(μ-dppm)₂(μ-Cl)(CO)₂]PF₆.     

Dta/TG study of the formation of the (Bi,Pb)2Sr2Ca2Cu3O10+δ superconductor

In order to get insight in some of the yet unanswered questions about the formation process of the (Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀₊ superconducting compound, coupled DTA-TG measurements have been performed in parallel with other techniques such as X-ray diffraction, Scanning Electron Microscopy and Energy Dispersive X-ray Microanalysis. The path leading to the formation of the (Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀₊ compound, starting from coprecipitated oxalates powders was studied. The activation energy of some of the involved transformation processes were determined. Relationships between the differences induced in the DTA traces by various sample nominal compositions and the intergranular magnetic properties of the superconductor will be discussed.     

Spectroscopic properties and hydration of the Cm(III) aqua ion from 10 to 85 °C

The optical absorption, fluorescence excitation, and emission spectra of the Cm(III) aqua ion in 0.001 M perchloric acid were studied in pure H(2)O, pure D(2)O, and in mixtures of H(2)O-D(2)O at temperatures from 10 to 85 °C. The quantum yield of the fluorescence of the Cm(III) aqua ion in pure H(2)O and D(2)O was also measured in this temperature range and the radiative decay rate constant was obtained from these data. The results indicate that, from 10 to 85 °C, the effect of temperature on the absorption, excitation, and emission spectra is very small. By correcting the observed decay rate constant for the radiative rate constant, a set of correlations between the observed fluorescence decay rate constant and the hydration number of Cm(3+) in H(2)O at temperatures from 10 to 85 °C was developed. A weak temperature dependence was observed for the nonradiative decay rate constant for the (6)D'(7/2)-(8)S'(7/2) transition and described by the Arrhenius equation. The activation energy of the nonradiative decay was measured to be 0.9 kJ mol(-1), approximately matching the energy gap between the first and the second (A(1) and A(2)) levels of the metastable (6)D'(7/2) multiplet of the Cm(III) aqua ion. On the basis of these observations, it is postulated that the slight increase in the observed fluorescence decay rate constant as the temperature increases from 10 to 85 °C is due to the effect of thermal population of the A(2) level.     

Stoichiometric to catalytic reactivity of the aryl cycloaurated species with arylboronic acids: insight into the mechanism of gold-catalyzed oxidative C(sp2)–H arylation

Based on the well-defined five-membered aryl gold(iii) complexes, [Au(tpy)X₂] (3a and 3b) and [AuBr(Ph)(tpy)] (7), as well as the aryl gold(iii) complex [AuCl₂(Ph)(tpy)] (8) (tpy = 2-(o-tolyl)pyridine) as reliable models, we present a detailed study of the mechanism for gold(iii)-catalyzed oxidative cross-coupling reactions between cycloaurable arenes and arylboronic acids. Here we report the direct evidence for a mechanistic proposal including arene C–H activation, transmetallation and biaryl reductive elimination. The chelation-assisted C–H activation strategy has been used for the development of the gold(iii)-catalyzed C–H bond arylation of arenes with aryl reagents to forge extended π-conjugated systems.     

An application of the PD(O)-catalyzed cyclocarbonylation of primary2-bromoallylamines to the synthesis of E- and Z-3-(hydroxyisopropylidene) azetidin-2-ones,useful precursors to a new class of monocyclic β-lactam antibiotics

Unprotected primary 2-bromoallylamines carrying a siloxy substituent undergo Pd(Ph₃P)₄-catalyzed cyclocarbonylation to give siloxy-substituted 3-isopropylideneazetidin-2-ones in good yield. These are readily desilylated to give the title compounds.     

Accessibility and Selective Stabilization of the Principal Spin States of Iron by Pyridyl versus Phenolic Ketimines: Modulation of the (6)A(1) ↔ (2)T(2) Ground-State Transformation of the [FeN(4)O(2)](+) Chromophore

Several potentially tridentate pyridyl and phenolic Schiff bases (apRen and HhapRen, respectively) were derived from the condensation reactions of 2-acetylpyridine (ap) and 2'-hydroxyacetophenone (Hhap), respectively, with N-R-ethylenediamine (RNHCH(2)CH(2)NH(2), Ren; R = H, Me or Et) and complexed in situ with iron(II) or iron(III), as dictated by the nature of the ligand donor set, to generate the six-coordinate iron compounds [Fe(II)(apRen)(2)]X(2) (R = H, Me; X(-) = ClO(4)(-), BPh(4)(-), PF(6)(-)) and [Fe(III)(hapRen)(2)]X (R = Me, Et; X(-) = ClO(4)(-), BPh(4)(-)). Single-crystal X-ray analyses of [Fe(II)(apRen)(2)](ClO(4))(2) (R = H, Me) revealed a pseudo-octahedral geometry about the ferrous ion with the Fe(II)-N bond distances (1.896-2.041 ?) pointing to the (1)A(1) (d(π)(6)) ground state; the existence of this spin state was corroborated by magnetic susceptibility measurements and M?ssbauer spectroscopy. In contrast, the X-ray structure of the phenolate complex [Fe(III)(hapMen)(2)]ClO(4), determined at 100 K, demonstrated stabilization of the ferric state; the compression of the coordinate bonds at the metal center is in accord with the (2)T(2) (d(π)(5)) ground state. Magnetic susceptibility measurements along with EPR and M?ssbauer spectroscopic techniques have shown that the iron(III) complexes are spin-crossover (SCO) materials. The spin transition within the [Fe(III)N(4)O(2)](+) chromophore was modulated with alkyl substituents to afford two-step and one-step (6)A(1) ? (2)T(2) transformations in [Fe(III)(hapMen)(2)]ClO(4) and [Fe(III)(hapEen)(2)]ClO(4), respectively. Previously, none of the X-salRen- and X-sal(2)trien-based ferric spin-crossover compounds exhibited a stepwise transition. The optical spectra of the LS iron(II) and SCO iron(III) complexes display intense d(π) → p(π)* and p(π) → d(π) CT visible absorptions, respectively, which account for the spectacular color differences. All the complexes are redox-active; as expected, the one-electron oxidative process in the divalent compounds occurs at higher redox potentials than does the reverse process in the trivalent compounds. The cyclic voltammograms of the latter compounds reveal irreversible electrochemical generation of the phenoxyl radical. Finally, the H(2)salen-type quadridentate ketimine H(2)hapen complexed with an equivalent amount of iron(III) to afford the μ-oxo-monobridged dinuclear complex [{Fe(III)(hapen)}(2)(μ-O)] exhibiting a distorted square-pyramidal geometry at the metal centers and considerable antiferromagnetic coupling of spins (J ≈ -99 cm(-1)).     

Functionalized 3(2H)-furanones via photooxygenation of (β-keto)-2-substituted furans: application to the biomimetic synthesis of merrekentrone C

Photooxygenation of (β-keto)-2-substituted furans leads, in a one pot operation, to functionalized 3(2H)-furanones with good to excellent yields. This methodology was applied as a key-step to the concise and biomimetic synthesis of the sesquiterpene merrekentrone C. The precursor to merrekentrone C, keto difuran, was synthesized using a cross coupling of α-iodo-3-acetylfuran with an alkenyl furan under Fenton-type conditions.     

Facile synthesis of nanoparticles of the molecule-based superconductor κ-(BEDT-TTF)2Cu(NCS)2

Well-dispersed roughly spherical nano-objects of the molecule-based superconductor κ-(BEDT-TTF)₂Cu(NCS)₂ have been prepared in an organic solution by using an easy synthetic route. Long alkyl-chain aconitate esters have been used as growth controlling agents. Nano-objects exhibiting sizes in the 35–120 nm range are made of aggregated individual smaller nanoparticles ranging from 3 to 10 nm. Nanoparticle powders have been studied by X-ray diffraction, high resolution electron microscopy and atomic force microscopy in the conductivity mode.     

The preparation and structure of the tetranuclear ruthenium cluster [Ru4(CO)10(μ2-Cl)2(μ3-OEt)2]

The tetranuclear ruthenium cluster [Ru₄(CO)₁₀Cl₂(OEt)₂] has been prepared in low yield by the reaction of [Ru₃(CO)₁₂] with [N(PPh₃)₂]Cl in refluxing EtOH, followed by oxidation with either [NO][BF₄] or Ag[ClO₄]. A single-crystal X-ray analysis of the complex shows that the four metal atoms adopt a planar geometry with one ruthenium bonded by two μ₂-Cl ligands and two μ₃-OEt ligands to a trinuclear fragment. This complex crystallises in the monoclinic space group I2/c, with a 14.458(3), b 22.073(6), c 15.302(4) Å, β 99.54(2)°, Z = 8; 3113 observed data with F > 3σ(F) were refined by blocked full-matrix least squares to R = 0.031, R_w = 0.034.     

Formation of ultracold Rb2 molecules in the v' = 0 level of the a(3)Σ+(u) state via blue-detuned photoassociation to the 1(3)Π(g) state

We report on the observation of blue-detuned photoassociation in Rb(2), in which vibrational levels are energetically above the corresponding excited atomic asymptote. (85)Rb atoms in a MOT were photoassociated at short internuclear distance to levels of the 1(3)Π(g) state at a rate of approximately 5 × 10(4) molecules s(-1). We have observed most of the predicted vibrational levels for all four spin-orbit components; 0(+)(g), 0(-)(g), 1(g), and 2(g), including levels of the 0(+)(g) outer well. These molecules decay to the metastable a(3)Σ(+)(u) state, some preferentially to the v' = 0 level, as we have observed for photoassociation to the v' = 8 level of the 1(g) component.     

Nucleophilic addition of alcohols to the C-N multiple bonds of the nitrilium substituent in the anion [2-B10H9(N≡CMe)]−

The reactions of salts of the anion [2-B₁₀H₉(N≡CMe)]⁻ with aliphatic alcohols ROH (R = C _n H_2n+1 (n = 1–6) CH₂CH₂(OEt), Prⁱ, Buⁱ, Bu^t, i-C₅H₁₁) are studied. These reactions result in hydrolytically stable imidates [2-B₁₀H₉{NH=C(OR)Me}]⁻. Their structures were confirmed by the data from mass spectrometry, IR, ¹H, ¹¹B, and ¹³C NMR spectroscopy. The molecular geometry of [2(Z)-B₁₀H₉{NH=C(OBu)Me}]⁻, which formed in nucleophilic addition reaction of n-butyl alcohol to [2-B₁₀H₉(N≡CMe)]⁻, was established by X-ray diffraction analysis.     

Improved and Scalable Synthetic Route to the Synthon 17-β-(2-Carboxyethyl)-1,3,5(10)-estratriene: An Important Intermediate in the Synthesis of Bone-Targeting Estrogens

An improved, highly scalable methodology for the multigram-scale preparation of an important synthon, 17-β-(2-carboxyethyl)-1,3,5(10)-estratriene, is described. Previous approaches have failed to provide useful quantities of the analytically pure product because of facile retro-Michael breakdown of the β-alkoxy carbonyl precursors during workup and isolation operations. The synthetic approach described herein has been designed specifically to sidestep this problematic breakdown process. This new scalable method of preparation overcomes a major hurdle in the exploration of structure–activity relationships centered around novel estradiol derivatives with bone-targeting properties and also provides a scalable process for subsequent developmental work.     

Reaction Mechanism of the Multi-channel Decomposition Reactions of C_(10)H_(14)~+·

n-Butylbenzene cations C10H14^＋ serve as a model compound to investigate the reaction mechanisms of alkylbenzene cations. The reactions of C10H14^＋. decomposition reaction system have been studied extensively at the B3LYP/6-311＋＋G^＊＊ level with Gaussion98 package. The chain reaction of C10H14^＋ dissociation was initiated by C-H bond rupture. All reaction channels initiated by C-H rupture were fully investigated with the vibrational mode analvsis to confirm the transition states and to reveal the reaction mechanism. A theoretical investigation on the reactions of this positive ion free radical can help us fully understand the decomposition processes.     

Diastereospecific addition of organometallics to (S)-2-alkoxy-1-(1,3-dithian-2-yl)-1-propanones and its application to the synthesis of (−)-trachelantic acid

Nucleophilic addition of organometallics to (S)-2-alkoxy-1-(1,3-dithian-2-yl)-1-propanones afforded preferentially (1R,2S)-2-alkoxy-1-alkyl-1-(1,3-dithian-2-yl)-1-propanols. The utility of the present reaction was demonstrated in the synthesis of (2R,3S)-trachelanthic acid.     

Application of the addition of triorganozincates to N-(tert-butanesulfinyl)imines to the enantioselective synthesis of α-amino acids

Highly enantiomerically enriched N-protected α-amino acids can be easily prepared from optically pure N-(tert-butanesulfinyl)imines by a four-step sequence involving: diastereoselective addition of a triorganozincate to the imine, removal of the sulfinyl group, benzoylation of the nitrogen atom of the obtained primary amine and oxidation of one of the substituents on the carbon atom α to the nitrogen. Using the same configuration in the sulfinyl chiral auxiliary, amino acids with the (R) or the (S) configuration can be prepared by choosing the proper combination of imine and organozincate. α,α-Disubstituted α-amino esters with high optical purity can also be prepared by the diastereoselective addition of trialkylzincates to α-imino esters.     

Electrochemical and Theoretical Investigations of the Role of the Appended Base on the Reduction of Protons by [Fe(2) (CO)(4) (κ(2) -PNP(R) )(μ-S(CH(2) )(3) S] (PNP(R) ={Ph(2) PCH(2) }(2) NR, R=Me, Ph)

The behavior of [Fe(2) (CO)(4) (κ(2) -PNP(R) )(μ-pdt)] (PNP(R) =(Ph(2) PCH(2) )(2) NR, R=Me (1), Ph (2); pdt=S(CH(2) )(3) S) in the presence of acids is investigated experimentally and theoretically (using density functional theory) in order to determine the mechanisms of the proton reduction steps supported by these complexes, and to assess the role of the PNP(R) appended base in these processes for different redox states of the metal centers. The nature of the R substituent of the nitrogen base does not substantially affect the course of the protonation of the neutral complex by CF(3) SO(3) H or CH(3) SO(3) H; the cation with a bridging hydride ligand, 1?μH(+) (R=Me) or 2?μH(+) (R=Ph) is obtained rapidly. Only 1?μH(+) can be protonated at the nitrogen atom of the PNP chelate by HBF(4) ?Et(2) O or CF(3) SO(3) H, which results in a positive shift of the proton reduction by approximately 0.15?V. The theoretical study demonstrates that in this process, dihydrogen can be released from a η(2) -H(2) species in the Fe(I) Fe(II) state. When R=Ph, the bridging hydride cation 2?μH(+) cannot be protonated at the amine function by HBF(4) ?Et(2) O or CF(3) SO(3) H, and protonation at the N atom of the one-electron reduced analogue is also less favored than that of a S atom of the partially de-coordinated dithiolate bridge. In this situation, proton reduction occurs at the potential of the bridging hydride cation, 2?μH(+) . The rate constants of the overall proton reduction processes are small for both complexes 1 and 2 (k(obs) ≈4-7?s(-1) ) because of the slow intramolecular proton migration and H(2) release steps identified by the theoretical study.