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1.
Fry HC Scaltrito DV Karlin KD Meyer GJ 《Journal of the American Chemical Society》2003,125(39):11866-11871
The observation and fast time-scale kinetic determination of a primary dioxygen-copper interaction have been studied. The ability to photorelease carbon monoxide from [Cu(I)(tmpa)(CO)](+) in mixtures of CO and O(2) in tetrahydrofuran (THF) between 188 and 218 K results in the observable formation of a copper-superoxide species, [Cu(II)(tmpa)(O(2)(-))](+) lambda(max) = 425 nm. Via this "flash-and-trap" technique, temperature-dependent kinetic studies on the forward reaction between dioxygen and [Cu(I)(tmpa)(thf)](+) afford activation parameters DeltaH = 7.62 kJ/mol and DeltaS = -45.1 J/mol K. The corresponding reverse reaction proceeds with DeltaH = 58.0 kJ/mol and DeltaS = 105 J/mol K. Overall thermodynamic parameters are DeltaH degrees = -48.5 kJ/mol and DeltaS degrees = -140 J/mol K. The temperature-dependent data allowed us to determine the room-temperature second-order rate constant, k(O2) = 1.3 x 10(9) M(-1) s(-1). Comparisons to copper and heme proteins and synthetic complexes are discussed. 相似文献
2.
This study details the electronic structure of the heme–peroxo–copper adduct {[(F8)Fe(DCHIm)]-O2-[Cu(AN)]}+ (LS(AN)) in which O2(2–) bridges the metals in a μ-1,2 or “end-on” configuration. LS(AN) is generated by addition of coordinating base to the parent complex {[(F8)Fe]-O2-[Cu(AN)]}+ (HS(AN)) in which the O2(2–) bridges the metals in an μ-η2:η2 or “side-on” mode. In addition to the structural change of the O2(2–) bridging geometry, coordination of the base changes the spin state of the heme fragment (from S = 5/2 in HS(AN) to S = 1/2 in LS(AN)) that results in an antiferromagnetically coupled diamagnetic ground state in LS(AN). The strong ligand field of the porphyrin modulates the high-spin to low-spin effect on Fe–peroxo bonding relative to nonheme complexes, which is important in the O–O bond cleavage process. On the basis of DFT calculations, the ground state of LS(AN) is dependent on the Fe–O–O–Cu dihedral angle, wherein acute angles (<~150°) yield an antiferromagnetically coupled electronic structure while more obtuse angles yield a ferromagnetic ground state. LS(AN) is diamagnetic and thus has an antiferromagnetically coupled ground state with a calculated Fe–O–O–Cu dihedral angle of 137°. The nature of the bonding in LS(AN) and the frontier molecular orbitals which lead to this magneto-structural correlation provide insight into possible spin topology contributions to O–O bond cleavage by cytochrome c oxidase. 相似文献
3.
Fukuzumi S Tahsini L Lee YM Ohkubo K Nam W Karlin KD 《Journal of the American Chemical Society》2012,134(16):7025-7035
The selective two-electron reduction of O(2) by one-electron reductants such as decamethylferrocene (Fc*) and octamethylferrocene (Me(8)Fc) is efficiently catalyzed by a binuclear Cu(II) complex [Cu(II)(2)(LO)(OH)](2+) (D1) {LO is a binucleating ligand with copper-bridging phenolate moiety} in the presence of trifluoroacetic acid (HOTF) in acetone. The protonation of the hydroxide group of [Cu(II)(2)(LO)(OH)](2+) with HOTF to produce [Cu(II)(2)(LO)(OTF)](2+) (D1-OTF) makes it possible for this to be reduced by 2 equiv of Fc* via a two-step electron-transfer sequence. Reactions of the fully reduced complex [Cu(I)(2)(LO)](+) (D3) with O(2) in the presence of HOTF led to the low-temperature detection of the absorption spectra due to the peroxo complex [Cu(II)(2)(LO)(OO)] (D) and the protonated hydroperoxo complex [Cu(II)(2)(LO)(OOH)](2+) (D4). No further Fc* reduction of D4 occurs, and it is instead further protonated by HOTF to yield H(2)O(2) accompanied by regeneration of [Cu(II)(2)(LO)(OTF)](2+) (D1-OTF), thus completing the catalytic cycle for the two-electron reduction of O(2) by Fc*. Kinetic studies on the formation of Fc*(+) under catalytic conditions as well as for separate examination of the electron transfer from Fc* to D1-OTF reveal there are two important reaction pathways operating. One is a rate-determining second reduction of D1-OTF, thus electron transfer from Fc* to a mixed-valent intermediate [Cu(II)Cu(I)(LO)](2+) (D2), which leads to [Cu(I)(2)(LO)](+) that is coupled with O(2) binding to produce [Cu(II)(2)(LO)(OO)](+) (D). The other involves direct reaction of O(2) with the mixed-valent compound D2 followed by rapid Fc* reduction of a putative superoxo-dicopper(II) species thus formed, producing D. 相似文献
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5.
Kenneth D. Karlin B. F. G. Johnson J. Lewis 《Journal of organometallic chemistry》1978,160(2):C21-C23
IR studies show that in solution aluminum trihalides form Lewis acid adducts at the iron atom in polyolefin tricarbonyliron complexes. A ketonic organometallic compound also forms a 2/1 adduct. 相似文献
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8.
Probability Theory and Related Fields - 相似文献
9.
S. Ansumali S. Arcidiacono S. S. Chikatamarla N. I. Prasianakis A. N. Gorban I. V. Karlin 《The European Physical Journal B - Condensed Matter and Complex Systems》2007,56(2):135-139
A general lattice Boltzmann method for simulation of
fluids with tailored transport coefficients is presented. It is
based on the recently introduced quasi-equilibrium kinetic models,
and a general lattice Boltzmann implementation is developed.
Lattice Boltzmann models for isothermal binary mixtures with a
given Schmidt number, and for a weakly compressible flow with a
given Prandtl number are derived and validated. 相似文献
10.
Conventional lattice Boltzmann models for the simulation of fluid dynamics are restricted by an error in the stress tensor that is negligible only for small flow velocity and at a singular value of the temperature. To that end, we propose a unified formulation that restores Galilean invariance and the isotropy of the stress tensor by introducing an extended equilibrium. This modification extends lattice Boltzmann models to simulations with higher values of the flow velocity and can be used at temperatures that are higher than the lattice reference temperature, which enhances computational efficiency by decreasing the number of required time steps. Furthermore, the extended model also remains valid for stretched lattices, which are useful when flow gradients are predominant in one direction. The model is validated by simulations of two- and three-dimensional benchmark problems, including the double shear layer flow, the decay of homogeneous isotropic turbulence, the laminar boundary layer over a flat plate and the turbulent channel flow. 相似文献