Snapshots of dioxygen activation by copper: the structure of a 1:1 Cu/O(2) adduct and its use in syntheses of asymmetric Bis(mu-oxo) complexes

The X-ray structure of a 1:1 Cu/O(2) adduct revealed side-on (eta(2)) O(2) coordination. Density functional calculations corroborated the structure, indicated a significant contribution of a Cu(III)-(O(2)(2-)) resonance form, and provided insights into the key bonding interactions. Reaction of a 1:1 adduct supported by a slightly different beta-diketiminate ligand with Cu(I) reagents resulted in the formation of novel asymmetric bis(mu-oxo) complexes that were identified by EPR, UV-vis, and Raman spectroscopy, as well as by an X-ray structure in one instance.     

A Validated TLC-Densitometric Method for the Simultaneous Determination of Formoterol Fumarate and Budesonide in Pressurized Metered-Dose Inhaler

JPC – Journal of Planar Chromatography – Modern TLC - A simple and robust thin-layer chromatography (TLC) method has been developed and validated for the simultaneous quantitative...     

Suppressing the spiking of a synchronized array of Izhikevich neurons

Nonlinear Dynamics - The aim of this research work is to investigate the synchronization and desynchronization of an array of non-identical Izhikevich neurons in a star-like configuration. Both...     

Ligand structural effects on Cu2S2 bonding and reactivity in side-on disulfido-bridged dicopper complexes

To assess supporting ligand effects on S-S bond activation, a series of [Cu2(mu-eta2:eta2-S2)]2+ complexes supported by various beta-diketiminate or anilido-imine ligands (L) were synthesized via the reaction of Cu(I) precursors LCu(CH(3)CN) with S8. For the cases where L = beta-diketiminate, the syntheses were complicated by formation of clusters [Cu(SR)]4, where SR represents the ligand functionalized by sulfur at the central methine position. The [Cu2(mu-eta2:eta2-S2)]2+ products were characterized by X-ray crystallography and electronic absorption and resonance Raman spectroscopy. Correlations among the Cu-S, Cu-Cu, and S-S distances and the nu(S-S) values were observed and interpreted within the framework of a previously described bonding picture (Chen, P.; Fujisawa, K.; Helton, M. E.; Karlin, K. D.; Solomon, E. I. J. Am. Chem. Soc. 2003, 125, 6394). Comparison of these data to those for other relevant species revealed a remarkable degree of S-S bond activation in the compounds supported by the beta-diketiminate and anilido-imine ligands, which through strong electron donation increase backbonding from the copper ions into the S-S sigma* orbital and cause S-S bond weakening. Reactions of one of the complexes supported by an anilido-imine ligand with PPh(3) and xylyl isocyanide were explored, revealing facile transfer of sulfur to PPh(3) but only displacement of sulfur to yield a LCu(I)-CNAr (Ar = xylyl) complex with the isocyanide.     

Mixed metal bis(mu-oxo) complexes with [CuM(mu-O)2]n+(M = Ni(III) or Pd(II)) cores

Two highly reactive heterodinuclear bis(mu-oxo) complexes were prepared by combining mononuclear peroxo species with reduced metal precursors at -80 degrees C and were identified by UV-vis, EPR/NMR, and resonance Raman spectroscopy, with corroboration in the case of the CuPd system from density functional calculations.     

Effects of thioether substituents on the O2 reactivity of beta-diketiminate-Cu(I) complexes: probing the role of the methionine ligand in copper monooxygenases

The activation of dioxygen by dopamine beta-monooxygenase (DbetaM) and peptidylglycine alpha-hydroxylating monooxygenase (PHM) is postulated to occur at a copper site ligated by two histidine imidazoles and a methionine thioether, which is unusual because such thioether ligation is not present in other O2-activating copper proteins. To assess the possible role of the thioether ligand in O2 activation by DbetaM and PHM, two new ligands comprising beta-diketiminates with thioether substituents were synthesized and Cu(I) and Cu(II) complexes were isolated. The Cu(II) compounds are monomeric and exhibit intramolecular thioether coordination. While the Cu(I) complexes exhibit a multinuclear topology in the solid state, variable-temperature 1H NMR studies implicate equilibria in solution, possibly including monomers with intramolecular thioether coordination that are structurally defined by DFT calculations. Low-temperature oxygenation of solutions of the Cu(I) complexes generates stable 1:1 Cu/O2 adducts, which on the basis of combined experimental and theoretical studies adopt side-on "eta(2)" structures with negligible Cu-thioether bonding and significant peroxo-Cu(III) character. In contrast to previously reported findings with related ligands lacking the thioether group, however (cf., Aboelella; et al. J. Am. Chem. Soc. 2004, 126, 16896), purging the solutions of the thioether-containing adducts with argon results in conversion to bis(mu-oxo)dicopper(III) species. A role for the thioether in promoting loss of O2 from the 1:1 Cu/O2 adduct and facilitating trapping of the resulting Cu(I) complex to yield the bis(mu-oxo) species is proposed, and the possible relevance of this role to that of the methionine in the active sites of DbetaM and PHM is discussed.     

A new class of (mu-eta2:eta2-disulfido)dicopper complexes: synthesis, characterization, and disulfido exchange

Rare examples of (mu-eta2:eta2-disulfido)dicopper complexes have been prepared from Cu(I) and Cu(II) complexes of beta-diketiminate and anilido-imine supporting ligands. A novel byproduct derived from sulfur functionalization of the methine position of a beta-diketiminate ligand was identified. DFT calculations on [(LCu)2X2] (L = beta-diketiminate, X = O or S) complexes rationalize the absence of a bis(mu-sulfido)dicopper isomer, [Cu2(mu-S)2](2+), in the synthetic reactions, yet predict that a [Cu2(mu-S)2](0) core is a stable product of 2-electron reduction of the [Cu2(mu-eta2:eta2-S2)](2+) unit. Exchange of the disulfido ligand was discovered upon reaction of a (mu-eta2:eta2-disulfido)dicopper complex with a Cu(I) reagent.     

On the rate of convergence of the Legendre spectral collocation method for multi-dimensional nonlinear Volterra-Fredholm integral equations

While the approximate solutions of one-dimensional nonlinear Volterra-Fredholm integral equations with smooth kermels are now well understood,no systematic studies of the numerical solutions of their multi-dimensional counterparts exist.In this paper,we provide an efficient numerical approach for the multi-dimensional nonlinear Volterra-Fredholm integral equations based on the multi-variate Legendre-collocation approach.Spectral collocation methods for multi-dimensional nonlinear integral equations are known to cause major difficulties from a convergence analysis point of view.Consequently,rigorous error estimates are provided in the weighted Sobolev space showing the exponential decay of the numerical errors.The existence and uniqueness of the numerical solution are established.Numerical experiments are provided to support the theoretical convergence analysis.The results indicate that our spectral collocation method is more flexible with better accuracy than the existing ones.     

Cytotoxic cembranoids from the Red Sea soft coral, Sarcophyton auritum

Chemical investigation of the Red Sea soft coral Sarcophyton auritum led to the isolation and structure elucidation of two new diterpene cembranoids; 2-epi-sarcophine (2) and (1R,2E,4S,6E,8R,11R,12R)-2,6-cembradiene-4,8,11,12-tetrol (4), as well as two known diterpene cembranoids, reported for the first time from this species, namely sarcophine (1) and (+)-7α,8β-dihydroxydeepoxysarcophine (3). Structure elucidation was achieved using spectroscopic techniques, including 1D and 2D NMR and HRMS. The isolated cembranoids were found to display high cytotoxicity against HepG2 (liver cancer cell line) and MCF-7 (breast cancer cell line).     

Electronic tuning of beta-diketiminate ligands with fluorinated substituents: effects on the O2-reactivity of mononuclear Cu(I) complexes

Copper(i) complexes with the beta-diketiminate ligands HC{C(R)N(Dipp)}{C(R')N(Dipp)}(-) (Dipp = C(6)H(3)(i)Pr(2-)2,6; L(1), R = CF(3), R' = CH(3); L(2), R = R' = CF(3)) have been isolated and fully characterized. On the basis of X-ray structural comparisons with the previously reported complex LCu(CH(3)CN) (L = HC{C(CH(3))N(Dipp)}(2)(-)), the ligand environments at the copper centers in the analogous nitrile adducts with L(1) and L(2) impose similar steric demands. L(1)Cu(CH(3)CN) reacts instantaneously at low temperature with O(2) to form a thermally-unstable intermediate with an isotope-sensitive vibration at 977 cm(-1) (928 cm(-1) with (18)O(2)), in accord with the peroxo O-O stretch associated with side-on coordination for LCu(O(2)). However, L(2)Cu(CH(3)CN) is unreactive toward O(2) even at room temperature. Evaluation of the redox potentials of the nitrile adducts and the CO stretching frequencies of the carbon monoxide adducts revealed an incremental adjustment of the electronic environment at the copper center that correlated with the extent of ligand fluorination. Furthermore, theoretical calculations (DFT, CASPT2) predicted that an increasing extent of Cu(ii)-superoxo character and end-on coordination of the O(2) moiety in the Cu/O(2) product (L(2) > L(1) > L) are accompanied by increases in the free energy for the oxygenation reaction, with L(2) unable to support a Cu/O(2) intermediate. Calculations also predict the 1 : 1 Cu/O(2) adducts to be unreactive with respect to hydrogen atom abstraction from hydrocarbon substrates on the basis of their stability towards both reduction and protonation.