Multielectron atom transfer reactions of perchlorate and other substrates catalyzed by rhenium oxazoline and thiazoline complexes: reaction kinetics, mechanisms, and density functional theory calculations

The title complexes, the Re(O)L(2)(Solv)(+) complexes (L = hoz, 2-(2'-hydroxyphenyl)-2-oxazoline(-) or thoz, 2-(2'-hydroxyphenyl)-2-thiazoline(-); Solv = H(2)O or CH(3)CN), are effective catalysts for the following fundamental oxo transfer reaction between closed shell molecules: XO + Y --> X + YO. Among suitable oxygen acceptors (Y's) are organic thioethers and phosphines, and among suitable oxo donors (XO's) are pyridine N-oxide (PyO), t-BuOOH, and inorganic oxyanions. One of the remarkable features of these catalysts is their high kinetic competency in effecting perchlorate reduction by pure atom transfer. Oxo transfer to rhenium(V) proceeds cleanly to afford the cationic dioxorhenium(VII) complex Re(O)(2)L(2)(+) in a two-step mechanism, rapid substrate (XO) coordination to give the precursor adduct cis-Re(V)(O)(OX)L(2)(+) followed by oxygen atom transfer (OAT) as the rate determining step. Electronic variations with PyO derivatives demonstrated that electron-withdrawing substituents accelerate the rate of Re(VII)(O)(2)L(2)(+) formation from the precursor adduct cis-Re(V)(O)(OX)L(2)(+). The activation parameters for OAT with picoline N-oxide and chlorate have been measured; the entropic barrier to oxo transfer is essentially zero. The potential energy surface for the reaction of Re(O)(hoz)(2)(OH(2))(+) with PyO was defined, and all pertinent intermediates and transition states along the reaction pathway were located by density functional theory (DFT) calculations (B3LYP/6-31G). In the second half of the catalytic cycle, Re(O)(2)L(2)(+) reacts with oxygen acceptors (Y's) in second-order reactions with associative transition states. The rate of OAT to substrates spans a remarkable range of 0.1-10(6) L mol(-)(1) s(-)(1), and the substrate reactivity order is Ph(3)P > dialkyl sulfides > alkyl aryl sulfides > Ph(2)S approximately DMSO, which demonstrates electrophilic oxo transfer. Competing deactivation and inhibitory pathways as well as their relevant kinetics are also reported.     

Flexible polyfluorinated bis-diazirines as molecular adhesives

Motivated by a desire to develop flexible covalent adhesives that afford some of the same malleability in the adhesive layer as traditional polymer-based adhesives, we designed and synthesized two flexible, highly fluorinated bis-diazirines. Both molecules are shown to function as effective crosslinkers for polymer materials, and to act as strong adhesives when painted between two polymer objects of low surface energy, prior to thermal activation. Data obtained from lap-shear experiments suggests that greater molecular flexibility is correlated with improved mechanical compliance in the adhesive layer.

Flexible, highly fluorinated covalent adhesives are synthesized, and are shown to afford comparable C–H insertion efficiency and adhesion strength relative to a rigid analogue, while providing improved mechanical compliance in the adhesion layer.     

Mechanism for reduction catalysis by metal oxo: hydrosilation of organic carbonyl groups catalyzed by a rhenium(V) oxo complex

The rhenium oxo complex [Re(O)(hoz)2][TFPB], 1 (where hoz = 2-(2'-hydroxyphenyl)-2-oxazoline(-) and TFPB = tetrakis(pentafluorophenyl)borate) catalyzes the hydrosilation of aldehydes and ketones under ambient temperature and atmosphere. The major organic product is the protected alcohol as silyl ether. Isolated yields range from 86 to 57%. The reaction requires low catalyst loading (0.1 mol %) and proceeds smoothly in CH2Cl2 as well as neat without solvent. In the latter condition, the catalyst precipitates at the end of reaction, allowing easy separation and catalyst recycling. Re(O)(hoz)(H), 3, was prepared, and its involvement in an ionic hydrosilation mechanism was evaluated. Complex 3 was found to be less hydridic than Et3SiH, refuting its participation in catalysis. A viable mechanism that is consistent with experimental findings, rate measurements, and kinetic isotope effects (Et3SiH/Et3SiD = 1.3 and benzaldehyde-H/benzaldehyde-D = 1.0) is proposed. Organosilane is activated via eta2-coordination to rhenium, and the organic carbonyl adds across the coordinated Si-H bond [2 + 2] to afford the organic reduction product.     

Active transient elasto-acoustic response damping of a thick-walled liquid-coupled piezolaminated cylindrical vessel

The linear 3D piezoelasticity theory in conjunction with the versatile transfer matrix approach and the wave equation for the internal acoustic domain are employed for active non-stationary vibroacoustic response control of an arbitrarily thick, tri-laminate, fluid-filled, simply supported, piezocomposite cylindrical tank, excited by arbitrary (non-axisymmetric) time-dependent on-surface mechanical loads. The smart structure is composed of a supporting core layer of functionally graded orthotropic material perfectly bonded to inner and outer spatially distributed radially polarized functionally graded piezoceramic sensor and uniform force actuator (FGPM) layers. Active vibration damping is implemented by transferring the accumulated voltage on the sensor layer to the piezoelectric actuator layer in context of proportional and derivative control laws. Durbin's numerical inverse Laplace transform scheme is utilized to calculate the time response histories of the relevant interface displacement/stress components, center-point acoustic pressure, and actuator voltage, for selected loading configurations (i.e., concentrated step, impulse, and moving external loads). Numerical simulations demonstrate the effectiveness of the adopted distributed sensing/actuation configuration together with the active damping control strategy in suppressing the vibroacoustic response of a three-layered (Ba₂NaNb₅O₁₅/Al/PZT4) water-filled piezoelastic cylindrical tank. Limiting cases are considered and the validity of results is established by comparison with the available data as well as with the aid of a commercial finite element package.     

Available and Waiting Times for Cognitive Radios

Cognitive radios (CRs) have been recently proposed for the problem of spectrum scarcity. The principle of CRs?? operation is based on the opportunistic access to the frequency spectrum mainly dedicated to primary users (PUs). The statistical time pattern of PUs?? channel usage and arrival can affect the usability of specific frequency bands for CRs. In this note, the effect of the arrival rate and channel holding time of PUs on the available times for CRs is analyzed. To this end, first, based on Poissonian arrivals, the available time for CRs is calculated. Then, assuming a gamma distribution for the inter-arrival times and a uniform distribution of channel holding time of PU in these intervals, the probability density function and moments of the available time for CRs are derived. Next, the effect of PUs statistical parameters on the average number of packets and the average symbol rate that a CR can transmit is analyzed. Also, taking that CR needs at least T seconds, the average waiting time is calculated.     

Facile,one-pot synthesis of new phenanthridine derivatives through 1,4-dipolar cycloaddition of phenantridine,activated acetylenes,and aromatic aldehydes

A facile, one-pot synthesis of new phenanthridine derivatives by a three-component reaction between phenantridine, dialkyl acetylenedicarboxylates（DAADs）, and aromatic aldehydes is described. The reaction is characterized by mild conditions, high selectivity, and tolerance to various functional groups.     

Mechanistic insight into the hydrogenation of acetylene on the Pd2/g-C3N4 catalyst: effect of Pd clustering on the barrier energy and selectivity

Structural Chemistry - In this work, the hydrogenation of acetylene on the Pd2/g-C3N4 catalyst is investigated by the density functional theory (DFT) and quantum theory of atoms in molecules...     

Supplier quality improvement: The value of information under uncertainty

We consider supplier development decisions for prime manufacturers with extensive supply bases producing complex, highly engineered products. We propose a novel modelling approach to support supply chain managers decide the optimal level of investment to improve quality performance under uncertainty. We develop a Poisson–Gamma model within a Bayesian framework, representing both the epistemic and aleatory uncertainties in non-conformance rates. Estimates are obtained to value a supplier quality improvement activity and assess if it is worth gaining more information to reduce epistemic uncertainty. The theoretical properties of our model provide new insights about the relationship between the degree of epistemic uncertainty, the effectiveness of development programmes, and the levels of investment. We find that the optimal level of investment does not have a monotonic relationship with the rate of effectiveness. If investment is deferred until epistemic uncertainty is removed then the expected optimal investment monotonically decreases as prior variance increases but only if the prior mean is above a critical threshold. We develop methods to facilitate practical application of the model to industrial decisions by a) enabling use of the model with typical data available to major companies and b) developing computationally efficient approximations that can be implemented easily. Application to a real industry context illustrates the use of the model to support practical planning decisions to learn more about supplier quality and to invest in improving supplier capability.