Product Protection, the Key to Developing High Performance Methane Selective Oxidation Catalysts

Selective, direct conversion of methane to methanol might seem an impossible task since the C−H bond energy of methane is 105 kcal mol^(−1) compared to the C−H bond energy for methanol of 94. We show here that the Catalytica catalyst is successful because the methanol is protected as methyl bisulfate, which is substantially less reactive than methanol toward the catalyst. This analysis suggests a limiting performance for systems that operate by this type of protection that is well above the Catalytica system

On the epistemic view of quantum states

We investigate the strengths and limitations of the Spekkens toy model, which is a local hidden variable model that replicates many important properties of quantum dynamics. First, we present a set of five axioms that fully encapsulate Spekkens' toy model. We then test whether these axioms can be extended to capture more quantum phenomena, by allowing operations on epistemic as well as ontic states. We discover that the resulting group of operations is isomorphic to the projective extended Clifford Group for two qubits. This larger group of operations results in a physically unreasonable model; consequently, we claim that a relaxed definition of valid operations in Spekkens' toy model cannot produce an equivalence with the Clifford Group for two qubits. However, the new operations do serve as tests for correlation in a two toy bit model, analogous to the well known Horodecki criterion for the separability of quantum states.Comment: 16 pages, 9 figure

Iridium complexes bearing a PNP ligand, favoring facile C(sp^3)–H bond cleavage

Hydrogen iodide is lost upon reaction of PNP with IrI_3, where PNP = 2,6-bis-(di-t-butylphosphinomethyl)pyridine to give crystallographically characterized Ir(PNP)*(I)_2, which reacts with H_2 to give Ir(PNP)(H)(I)_2. Ir(PNP)(Cl)_3 is relatively inert towards the intramolecular C–H activation of the tert-butyl's of the PNP ligand

Entanglement of subspaces in terms of entanglement of superpositions

We investigate upper and lower bounds on the entropy of entanglement of a superposition of bipartite states as a function of the individual states in the superposition. In particular, we extend the results in [G. Gour, arxiv.org:0704.1521 (2007)] to superpositions of several states rather than just two. We then investigate the entanglement in a subspace as a function of its basis states: we find upper bounds for the largest entanglement in a subspace and demonstrate that no such lower bound for the smallest entanglement exists. Finally, we consider entanglement of superpositions using measures of entanglement other than the entropy of entanglement.Comment: 7 pages, no figure

Effects of Companies’ Initiatives to Reduce Early Retirement Among Older Workers

Although active ageing policy and practice vary between countries, we believe that knowledge about the effects of Norwegian companies’ initiatives to delay early retirement is of interest for all countries striving to increase the employment rates of older workers. Since the agreement on a more inclusive working life (IW agreement) was signed in 2001, the Norwegian government and social partners have encouraged companies to develop a more senior-friendly policy and implement special measures to retain older workers. In this article, we evaluate the effects of such measures. Our research question is, have preventive measures offered by companies to employees aged 62 years and older contributed to reduced rates of early retirement? We use a ‘difference-in-differences’ approach and examine whether measures at the company level to counteract early retirement actually affect older employees’ retirement decisions, controlling for different individual and enterprise factors. This is done by comparing changes and differences in the individual likelihood of early retirement on the contractual pension (AFP scheme) and disability pension in the period 2002–2007 among employees 62 years of age in businesses with and without the corresponding preventive measures/instruments. The analyses show that the likelihood that a 62-year-old worker will retire on the AFP scheme has increased from 2002 to 2007. This applies equally to 62-year-old employees in enterprises that have enacted special measures to retain older workers as well as 62-year-olds in enterprises that have not enacted any such measures. On the other hand, the likelihood that a 62-year-old worker will retire because of disability decreased from 2002 to 2007, among employees in both the intervention enterprises and the control enterprises. However, when controlling for other relevant characteristics of individuals and enterprises, the analysis indicates that the measures as such have had no effect on the likelihood of 62-year-olds retiring

The para-substituent effect and pH-dependence of the organometallic Baeyer–Villiger oxidation of rhenium–carbon bonds

We studied the Baeyer–Villiger (BV) type oxidation of phenylrhenium trioxide (PTO) by H2O2 in the aqueous phase using Quantum Mechanics (density functional theory with the M06 functional) focusing on how the solution pH and the para-substituent affect the Gibbs free energy surfaces. For both PTO and MTO (methylrhenium trioxide) cases, we find that for pH > 1 the BV pathway having OH− as the leaving group is lower in energy than the one involving simultaneous protonation of hydroxide. We also find that during this organometallic BV oxidation, the migrating phenyl is a nucleophile so that substituting functional groups in the para-position of phenyl with increased electron-donating character lowers the migration barrier, just as in organic BV reactions. However, this substituent effect also pushes electron density to Re, impeding HOO− coordination and slowing down the reaction. This is in direct contrast to the organic analog, in which para-substitution has an insignificant influence on 1,2-addition of peracids. Due to the competition of the two opposing effects and the dependence of the resting state on pH and concentration, the reaction rate of the organometallic BV oxidation is surprisingly unaffected by para-substitution

Functionalization of Rhenium Aryl Bonds by O-Atom Transfer

Aryltrioxorhenium (ArReO_3) has been demonstrated to show rapid oxy-functionalization upon reaction with O-atom donors, YO, to selectively generate the corresponding phenols in near quantitative yields. (18)^O-Labeling experiments show that the oxygen in the products is exclusively from YO. DFT studies reveal a 10.7 kcal/mol barrier (Ar = Ph) for oxy-functionalization with H_2O_2 via a Baeyer-Villiger type mechanism involving nudeophilic attack of the aryl group on an electrophilic oxygen of YO coordinated to rhenium

Storing entanglement of nuclear spins via Uhrig Dynamical Decoupling

Stroboscopic spin flips have already been shown to prolong the coherence times of quantum systems under noisy environments. Uhrig's dynamical decoupling scheme provides an optimal sequence for a quantum system interacting with a dephasing bath. Several experimental demonstrations have already verified the efficiency of such dynamical decoupling schemes in preserving single qubit coherences. In this work we describe the experimental study of Uhrig's dynamical decoupling in preserving two-qubit entangled states using an ensemble of spin-1/2 nuclear pairs in solution state. We find that the performance of odd-order Uhrig sequences in preserving entanglement is superior to both even-order Uhrig sequences and periodic spin-flip sequences. We also find that there exists an optimal length of the Uhrig sequence at which the decoherence time gets boosted from a few seconds to about 30 seconds.Comment: 6 pages, 7 figure

Synthesis and Characterization of the k^2-acac-O,O Complex Os_(IV)(acac)_2PhCl and Study of CH Activation with Benzene

We have synthesized and fully characterized the air-stable complex (κ^2-acac-O,O)2Os^(IV)(Ph)Cl (Cl-1-Ph; acac-O,O = acetylacetonate), which reacts with C_6D_6 to generate Cl-1-Ph-d_5 in high yield and catalyzes the H/D exchange reaction between benzene and toluene-d_8 upon heating to 140 °C. To our knowledge, this is the first example of stoichiometric and catalytic, homogeneous, intermolecular CH activation of arenes by a discrete Os complex. The reactions show extended induction periods. DFT studies of Cl-1-Ph and cis-(κ^2-acac-O,O)_2Os^(III)(C_6H_5)(C_6D_6) (cis-(C_6D_6)-2-Ph) found a mechanism involving CH activation by traces of Os(III) and Cl atom transfer between Cl-1-Ph and cis-(C_6D_6)-2-Ph. Experimental data showing that addition of reductants eliminates the induction periods suggest that CH activation occurs from an oxidation state lower than Os^(IV), consistent with the DFT predictions. Consistent with a Cl atom transfer mechanism, the triflate analogue of Cl-1-Ph, OTf-1-Ph, does not undergo a stoichiometric or catalytic reaction with C_6D_6