α-Alkylation and Asymmetric Transfer Hydrogenation of Tetralone via Hydrogen Borrowing and Dynamic Kinetic Resolution Strategy Using a Single Iridium(III) Complex.

Here we present a novel strategy for the synthesis of enantiomerically enriched tetrahydronaphthalen-1-ols. The reaction proceeds via an alkylation (via hydrogen borrowing) and ammonium formate-mediated asymmetric transfer hydrogenation (via dynamic kinetic resolution), giving alkylated tetralols in high yields and good enantio- and diastereoselectivity across a diverse range of both alcohol and tetralone substrates. Additionally, these products were successfully derivatized to several complex molecules, demonstrating the utility of the tetrahydronaphthalen-1-ol.

Cosmological inflation and meta-empirical theory assessment.

I apply Dawid's Meta-Empirical Assessment (MEA) methodology to the theory of cosmological inflation. I argue that applying this methodology does not currently offer a compelling case for ascribing non-empirical confirmation to cosmological inflation. In particular, I argue that despite displaying strong instances of Unexpected Explanatory Coherence (UEA), it is premature to evaluate the theory on the basis of the No Alternatives Argument (NAA). More significantly though, I argue that the theory of cosmological inflation fails to sustain a convincing Meta-Inductive Argument (MIA) because the empirical evidence and theoretical successes that it seeks to draw meta-empirical support from do not warrant a meta-inductive inference to inflation. I conclude by assessing how future developments could pave the way towards crafting a more compelling case for the non-empirical confirmation of cosmological inflation.

Methodological reflections on the MOND/dark matter debate.

The paper re-examines the principal methodological questions, arising in the debate over the cosmological standard model's postulate of Dark Matter vs. rivalling proposals that modify standard (Newtonian and general-relativistic) gravitational theory, the so-called Modified Newtonian Dynamics (MOND) and its subsequent extensions. What to make of such seemingly radical challenges of cosmological orthodoxy? In the first part of our paper, we assess MONDian theories through the lens of key ideas of major 20th century philosophers of science (Popper, Kuhn, Lakatos, and Laudan), thereby rectifying widespread misconceptions and misapplications of these ideas common in the pertinent MOND-related literature. None of these classical methodological frameworks, which render precise and systematise the more intuitive judgements prevalent in the scientific community, yields a favourable verdict on MOND and its successors-contrary to claims in the MOND-related literature by some of these theories' advocates; the respective theory appraisals are largely damning. Drawing on these insights, the paper's second part zooms in on the most common complaint about MONDian theories, their ad-hocness. We demonstrate how the recent coherentist model of ad-hocness captures, and fleshes out, the underlying-but too often insufficiently articulated-hunches underlying this critique. MONDian theories indeed come out as severely ad hoc: they do not cohere well with either theoretical or empirical-factual background knowledge. In fact, as our complementary comparison with the cosmological standard model's Dark Matter postulate shows, with respect to ad-hocness, MONDian theories fare worse than the cosmological standard model.

Edge Modes and Dressing Fields for the Newton-Cartan Quantum Hall Effect.

It is now well-known that Newton-Cartan theory is the correct geometrical setting for modelling the quantum Hall effect. In addition, in recent years edge modes for the Newton-Cartan quantum Hall effect have been derived. However, the existence of these edge modes has, as of yet, been derived using only orthodox methodologies involving the breaking of gauge-invariance; it would be preferable to derive the existence of such edge modes in a gauge-invariant manner. In this article, we employ recent work by Donnelly and Freidel in order to accomplish exactly this task. Our results agree with known physics, but afford greater conceptual insight into the existence of these edge modes: in particular, they connect them to subtle aspects of Newton-Cartan geometry and pave the way for further applications of Newton-Cartan theory in condensed matter physics.

Standard Sirens as a Novel Probe of Dark Energy.

Cosmological models with a dynamical dark energy field typically lead to a modified propagation of gravitational waves via an effectively time-varying gravitational coupling G(t). The local variation of this coupling between the time of emission and detection can be probed with standard sirens. Here we discuss the role that lunar laser ranging (LLR) and binary pulsar constraints play in the prospects of constraining G(t) with standard sirens. In particular, we argue that LLR constrains the matter-matter gravitational coupling G_{N}(t), whereas binary pulsars and standard sirens constrain the quadratic kinetic gravity self-interaction G_{gw}(t). Generically, these two couplings could be different in alternative cosmological models, in which case LLR constraints are irrelevant for standard sirens. We use the Hulse-Taylor pulsar data and show that observations are highly insensitive to time variations of G_{gw}(t) yet highly sensitive to G_{N}(t). We thus conclude that future gravitational waves data will become the best probe to test G_{gw}(t), and will hence provide novel constraints on dynamical dark energy models.

An Efficient Synthesis of Geminal-Dialkyl Dienes for Olefin Metathesis Polymerization.

A robust synthesis of gem-dialkyl acyclic diene monomers has been developed. This route is scalable, flexible, and biorenewable, allowing for the production of a wide range of diene monomers of different lengths and different gem-dialkyl substitution starting from unsaturated esters derived from seed oils. The metathesis polymerization of these monomers and the hydrogenation of the resulting polyolefins leads to telechelic gem-dialkyl polyethylenes, which can be used as elastomers in the synthesis of polyurethanes and other block polymers.

Examining the Effects of Monomer and Catalyst Structure on the Mechanism of Ruthenium-Catalyzed Ring-Opening Metathesis Polymerization.

The mechanism of Ru-catalyzed ring-opening metathesis polymerization (ROMP) is studied in detail using a pair of third generation ruthenium catalysts with varying sterics of the N-heterocyclic carbene (NHC) ligand. Experimental evidence for polymer chelation to the Ru center is presented in support of a monomer-dependent mechanism for polymerization of norbornene monomers using these fast-initiating catalysts. A series of kinetic experiments, including rate measurements for ROMP, rate measurements for initiation, monomer-dependent kinetic isotope effects, and activation parameters were useful for distinguishing chelating and nonchelating monomers and determining the effect of chelation on the polymerization mechanism. The formation of a chelated metallacycle is enforced by both the steric bulk of the NHC and by the geometry of the monomer, leading to a ground-state stabilization that slows the rate of polymerization and also alters the reactivity of the propagating Ru center toward different monomers in copolymerizations. The results presented here add to the body of mechanistic work for olefin metathesis and may inform the continued design of catalysts for ROMP to access new polymer architectures and materials.

Room-temperature cycling of metal fluoride electrodes: Liquid electrolytes for high-energy fluoride ion cells.

Fluoride ion batteries are potential "next-generation" electrochemical storage devices that offer high energy density. At present, such batteries are limited to operation at high temperatures because suitable fluoride ion-conducting electrolytes are known only in the solid state. We report a liquid fluoride ion-conducting electrolyte with high ionic conductivity, wide operating voltage, and robust chemical stability based on dry tetraalkylammonium fluoride salts in ether solvents. Pairing this liquid electrolyte with a copper-lanthanum trifluoride (Cu@LaF3) core-shell cathode, we demonstrate reversible fluorination and defluorination reactions in a fluoride ion electrochemical cell cycled at room temperature. Fluoride ion-mediated electrochemistry offers a pathway toward developing capacities beyond that of lithium ion technology.

High-spatial-resolution mapping of catalytic reactions on single particles.

The critical role in surface reactions and heterogeneous catalysis of metal atoms with low coordination numbers, such as found at atomic steps and surface defects, is firmly established. But despite the growing availability of tools that enable detailed in situ characterization, so far it has not been possible to document this role directly. Surface properties can be mapped with high spatial resolution, and catalytic conversion can be tracked with a clear chemical signature; however, the combination of the two, which would enable high-spatial-resolution detection of reactions on catalytic surfaces, has rarely been achieved. Single-molecule fluorescence spectroscopy has been used to image and characterize single turnover sites at catalytic surfaces, but is restricted to reactions that generate highly fluorescing product molecules. Herein the chemical conversion of N-heterocyclic carbene molecules attached to catalytic particles is mapped using synchrotron-radiation-based infrared nanospectroscopy with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. These observations demonstrate that, compared to the flat regions on top of the particles, the peripheries of the particles-which contain metal atoms with low coordination numbers-are more active in catalysing oxidation and reduction of chemically active groups in surface-anchored N-heterocyclic carbene molecules.

Phosphonium Formation by Facile Carbon-Phosphorus Reductive Elimination from Gold(III).

A recent trend in homogeneous gold catalysis has been the development of oxidative transformations relying on Au(I)/Au(III) redox cycling. Typically, phosphine-supported Au(I) precatalysts are used in the presence of strong oxidants to presumably generate phosphine Au(III) intermediates. Herein, we disclose that such Au(III) complexes can undergo facile C(aryl)-P reductive elimination to afford phosphonium salts, which have been spectroscopically and crystallographically characterized. Mechanistic studies indicate that this process occurs from cationic species at temperatures as low as -20 °C but can be accelerated in the presence of nucleophiles, such as acetonitrile and phosphines, via a five-coordinate intermediate. Importantly, this study highlights that irreversible C(aryl)-P reductive elimination is a feasible decomposition or activation pathway for phosphine-supported Au(III) catalysts and should not be ignored in future reaction development.

Halide-Dependent Mechanisms of Reductive Elimination from Gold(III).

Two unique organometallic halide series (Ph3P)Au(4-Me-C6H4)(CF3)(X) and (Cy3P)Au(4-F-C6H4)(CF3)(X) (X = I, Br, Cl, F) have been synthesized. The PPh3-supported complexes can undergo both C(aryl)-X and C(aryl)-CF3 reductive elimination. Mechanistic studies of thermolysis at 122 °C reveal a dramatic reactivity and kinetic selectivity dependence on halide ligand. For X = I or F, zero-order kinetic behavior is observed, while for X = Cl or Br, kinetic studies implicate product catalysis. The selectivity for C(aryl)-CF3 bond formation increases in the order X = I < Br < Cl < F, with exclusively C(aryl)-I bond formation when X = I, and exclusively C(aryl)-CF3 bond formation when X = F. Thermodynamic measurements show that Au(III)-X bond dissociation energies increase in the order X = I < Br < Cl, and that ground state Au(III)-X bond strength ultimately dictates selectivities for C(aryl)-X and C(aryl)-CF3 reductive elimination.

Photoinitiated oxidative addition of CF3I to gold(I) and facile aryl-CF3 reductive elimination.

Herein we report the mechanism of oxidative addition of CF3I to Au(I), and remarkably fast Caryl-CF3 bond reductive elimination from Au(III) cations. CF3I undergoes a fast, formal oxidative addition to R3PAuR' (R = Cy, R' = 3,5-F2-C6H4, 4-F-C6H4, C6H5, 4-Me-C6H4, 4-MeO-C6H4, Me; R = Ph, R' = 4-F-C6H4, 4-Me-C6H4). When R' = aryl, complexes of the type R3PAu(aryl)(CF3)I can be isolated and characterized. Mechanistic studies suggest that near-ultraviolet light (λmax = 313 nm) photoinitiates a radical chain reaction by exciting CF3I. Complexes supported by PPh3 undergo reversible phosphine dissociation at 110 °C to generate a three-coordinate intermediate that undergoes slow reductive elimination. These processes are quantitative and heavily favor Caryl-I reductive elimination over Caryl-CF3 reductive elimination. Silver-mediated halide abstraction from all complexes of the type R3PAu(aryl)(CF3)I results in quantitative formation of Ar-CF3 in less than 1 min at temperatures as low as -10 °C.

Exceptionally fast carbon-carbon bond reductive elimination from gold(III).

Reductive elimination of carbon-carbon bonds occurs in numerous metal-catalysed reactions. This process is well documented for a variety of transition metal complexes. However, carbon-carbon bond reductive elimination from a limited number of Au(III) complexes has been shown to be a slow and prohibitive process that generally requires elevated temperatures. Herein we show that oxidation of a series of mono- and bimetallic Au(I) aryl complexes at low temperature generates observable Au(III) and Au(II) intermediates. We also show that aryl-aryl bond reductive elimination from these oxidized species is not only among the fastest observed for any transition metal, but is also mechanistically distinct from previously studied alkyl-alkyl and aryl-alkyl reductive eliminations from Au(III).

Bis(η-naphthalene)-molybdenum(0).

The title compound, [Mo(C(10)H(8))(2)], was prepared from the naphthalene radical anion and MoCl(4)(thf)(2) (thf is tetra-hydro-furan). In the crystal, the mol-ecule is located on an inversion center. The Mo atom is equally disordered over two positions; the range of Mo-C distances is 2.2244 (19)-2.3400 (17) Šfor both components of the disorder.