Persistence of the three-state description of mixed valency at the localized-to-delocalized transition

Application of a semiclassical three-state model of mixed valency to complexes of the type [Ru(3)(μ(3)-O)(OAc)(6)(CO)(py)-(μ(2)-BL)-Ru(3)(μ(3)-O)(OAc)(6)(CO)(py)](-1), where BL = 1,4-pyrazine or 4,4'-bipyridine and py = 4-dimethylaminopyridine, pyridine, or 4-cyanopyridine is described. The appearance of two intervalence charge transfer (IVCT) bands in the near-infrared (NIR) region of the electronic spectra of these complexes is explained well by the three-state model. An important feature of the three-state model is that the IVCT band evolves into two bands: one that is metal-to-bridging-ligand-charge-transfer (MBCT) in character and another that is metal-to-metal-charge-transfer (MMCT) in character. The three-state model also fully captures the observed spectroscopic behavior in which the MBCT transition increases in energy and the MMCT band decreases in energy with increasing electronic communication in a series of mixed valence ions. The appearance of both the MBCT and MMCT bands is found to persist as coalescence of infrared (IR) vibrational spectra suggest a ground state delocalized on the picosecond time scale. The solvent and temperature dependence of the MBCT and MMCT electronic transitions defines the mixed valence complexes reported here as lying on the borderline of delocalization.     

Electrocatalytic oxidation of formate by [Ni(P(R)2N(R')2)2(CH3CN)]2+ complexes

[Ni(P(R)(2)N(R')(2))(2)(CH(3)CN)](2+) complexes with R = Ph, R' = 4-MeOPh or R = Cy, R' = Ph , and a mixed-ligand [Ni(P(R)(2)N(R')(2))(P(R'(2))N(R'(2)))(CH(3)CN)](2+) with R = Cy, R' = Ph, R' = Ph, have been synthesized and characterized by single-crystal X-ray crystallography. These and previously reported complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO(2), protons, and electrons, with rates that are first-order in catalyst and formate at formate concentrations below ～0.04 M (34 equiv). At concentrations above ～0.06 M formate (52 equiv), catalytic rates become nearly independent of formate concentration. For the catalysts studied, maximum observed turnover frequencies vary from <1.1 to 15.8 s(-1) at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. These catalysts are the only base-metal electrocatalysts as well as the only homogeneous electrocatalysts reported to date for the oxidation of formate. An acetate complex demonstrating an η(1)-OC(O)CH(3) binding mode to nickel has also been synthesized and characterized by single-crystal X-ray crystallography. Based on this structure and the electrochemical and spectroscopic data, a mechanistic scheme for electrocatalytic formate oxidation is proposed which involves formate binding followed by a rate-limiting proton and two-electron transfer step accompanied by CO(2) liberation. The pendant amines have been demonstrated to be essential for electrocatalysis, as no activity toward formate oxidation was observed for the similar [Ni(depe)(2)](2+) (depe = 1,2-bis(diethylphosphino)ethane) complex.     

Dinuclear Complexes of Copper(I) with Crown Ether‐containing N‐Thiophosphorylated Bis‐thioureas and 2,2′‐Bipyridine or 1,10‐Phenanthroline: Synthesis,Characterization, and Picrate Extraction Properties

Reaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N‐thiophosphorylated bis‐thioureas N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 ( H₂L^I ), N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐18‐crown‐6 ( H₂L^II ) and N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐15‐crown‐5 ( H₂L^III ). Reaction of the potassium salts of H₂L^I–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH₂Cl₂ leads to the dinuclear complexes [Cu₂(bpy)₂L^I–III] and [Cu₂(phen)₂L^I–III] . The structures of these compounds were investigated by ¹H, ³¹P{¹H} NMR spectroscopy, and elemental analysis. The crystal structures of H₂L^I and [Cu₂(phen)₂L^I] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(=CMe₂)CH₂P(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH₄Pic were also studied.     

Mathematical programming modeling of the Response Time Variability Problem

The Response Time Variability Problem (RTVP) is a scheduling problem that has recently been defined in the literature. The RTVP has a broad range of real-life applications from manufacturing to services and information technology. A previous study developed a position exchange heuristic to apply to initial sequences for the RTVP, and a MILP (Mixed Integer Linear Programming) to obtain optimal solutions with a practical limit of 25 units to be scheduled. This paper aims to improve the best mathematical programming model developed thus far in order to solve larger instances up to 40 units to optimality. The contribution of this paper is 4-fold: (i) larger instances can be solved to optimality by the off the shelf standard software; (ii) the new optimal solutions of the RTVP can be used to compare the results of heuristic procedures; (iii) the importance of modeling is demonstrated, as well as the huge impact that reformulation, redundant constraints and the elimination of symmetries have on the efficiency of MILPs is clearly established; finally (iv) a challenge to develop a customized optimization algorithm to rival the MILP solution efficiency for the RTVP is put forward.     

Oxidation and thermal annealing effects on native and ion-irradiated PbTe films grown by molecular beam deposition

Investigations are reported into the effect of low-pressure oxygen exposure and thermal annealing on the carrier transport properties of native and 350 eV Ar⁺ bombarded PbTe films. The electrical measurements were madein situ on MBD-grown PbTe films without breaking vacuum. On native surfaces, oxidation was initially sustained by diffusion of a donor species from the film bulk to the surface, where reaction with oxygen occured. This diffusion process was apparently inhibited on ion irradiated films and direct doping of the film surface effected a gradual reduction in the ion-induced electron accumulation resident at the film surface. The native properties and behavioural characteristics of the films could be recovered by thermal annealing of the ion-irradiated and/or oxidized films at 300–350 °C.     

Potentiometric titration of hydroxide,aluminate and carbonate in sodium aluminate solutions

An automated potentiometric titration of hydroxide, aluminate and carbonate in sodium aluminate solutions is described. The addition of barium chloride before titration with hydrochloric acid enables the three components to be determined in one run, involving neutralization of hydroxide, protonation of aluminate and dissolution of barium carbonate. The accuracy and precision of the method are satisfactory for a rapid method used for control of aluminum oxide production.     

Hydrocarbation chemistry proceeding from nickel carbenes

Nickel carbene complex 2 [Ni(triphos)C(H)N(H)xylyl]2+(BF4-)2 reacts with alkenes quantitatively and regiospecifically to give the anti-Markovnikov hydrocarbation products. X-ray crystallography shows significant iminium alkyl character of the hydrocarbation products, similar to that observed in parent carbene 2. Mechanistic studies suggest the importance of a "hydride" pathway over "alkene" (metallocycle formation or carbocation) pathways.