Thermal vesiculation during volcanic eruptions.

Terrestrial volcanic eruptions are the consequence of magmas ascending to the surface of the Earth. This ascent is driven by buoyancy forces, which are enhanced by bubble nucleation and growth (vesiculation) that reduce the density of magma. The development of vesicularity also greatly reduces the 'strength' of magma, a material parameter controlling fragmentation and thus the explosive potential of the liquid rock. The development of vesicularity in magmas has until now been viewed (both thermodynamically and kinetically) in terms of the pressure dependence of the solubility of water in the magma, and its role in driving gas saturation, exsolution and expansion during decompression. In contrast, the possible effects of the well documented negative temperature dependence of solubility of water in magma has largely been ignored. Recently, petrological constraints have demonstrated that considerable heating of magma may indeed be a common result of the latent heat of crystallization as well as viscous and frictional heating in areas of strain localization. Here we present field and experimental observations of magma vesiculation and fragmentation resulting from heating (rather than decompression). Textural analysis of volcanic ash from Santiaguito volcano in Guatemala reveals the presence of chemically heterogeneous filaments hosting micrometre-scale vesicles. The textures mirror those developed by disequilibrium melting induced via rapid heating during fault friction experiments, demonstrating that friction can generate sufficient heat to induce melting and vesiculation of hydrated silicic magma. Consideration of the experimentally determined temperature and pressure dependence of water solubility in magma reveals that, for many ascent paths, exsolution may be more efficiently achieved by heating than by decompression. We conclude that the thermal path experienced by magma during ascent strongly controls degassing, vesiculation, magma strength and the effusive-explosive transition in volcanic eruptions.

Nickel-Mediated Cross-Coupling of Boronic Acids and Phthalimides for the Synthesis of Ortho-Substituted Benzamides.

The decarbonylative coupling of phthalimides with aryl boronic acids provides ready access to a broad range of ortho-substituted benzamides. This nickel-mediated methodology extends reactivity from previously described air-sensitive diorganozinc reagents of limited availability to easily handled and widely commercially available boronic acids. The decarbonylative coupling is tolerant of a broad range of functional groups and demonstrates little sensitivity to steric factors on either of the coupling partners.

Oxidative coupling of Michael acceptors with aryl nucleophiles produced through rhodium-catalyzed C-C bond activation.

Utilizing rhodium catalysis, aryl nucleophiles generated via carbon-carbon single bond activation successfully undergo oxidative coupling with Michael acceptors. The reaction scope encompasses a broad range of nucleophiles generated from quinolinyl ketones as well as a series of electron deficient terminal alkenes, illustrating the broad potential of intersecting carbon-carbon bond activation with synthetically useful coupling methodologies. The demonstrated oxidative coupling produces a range of cinnamyl derivatives, several of which are challenging to prepare via conventional routes.

Long-period earthquakes and co-eruptive dome inflation seen with particle image velocimetry.

Dome growth and explosive degassing are fundamental processes in the cycle of continental arc volcanism. Because both processes generate seismic energy, geophysical field studies of volcanic processes are often grounded in the interpretation of volcanic earthquakes. Although previous seismic studies have provided important constraints on volcano dynamics, such inversion results do not uniquely constrain magma source dimension and material properties. Here we report combined optical geodetic and seismic observations that robustly constrain the sources of long-period volcanic earthquakes coincident with frequent explosive eruptions at the volcano Santiaguito, in Guatemala. The acceleration of dome deformation, extracted from high-resolution optical image processing, is shown to be associated with recorded long-period seismic sources and the frequency content of seismic signals measured across a broadband network. These earthquake sources are observed as abrupt subvertical surface displacements of the dome, in which 20-50-cm uplift originates at the central vent and propagates at approximately 50 m s(-1) towards the 200-m-diameter periphery. Episodic shifts of the 20-80-m thick dome induce peak forces greater than 10(9) N and reflect surface manifestations of the volcanic long-period earthquakes, a broad class of volcano seismic activity that is poorly understood and observed at many volcanic centres worldwide. On the basis of these observations, the abrupt mass shift of solidified domes, conduit magma or magma pads may play a part in generating long-period earthquakes at silicic volcanic systems.

Steric and electronic effects influencing ß-aryl elimination in the Pd-catalyzed carbon-carbon single bond activation of triarylmethanols.

An analysis of the palladium-catalyzed activation of carbon-carbon single bonds within triarylmethanols has led to a greater understanding of factors influencing the ß-aryl elimination process responsible for C-C bond cleavage. A series of competition reactions were utilized to determine that ß-aryl elimination of aryl substituents containing ortho-substitution proceeds with significant preference to unsubstituted phenyl rings. Further experiments indicate that substrates containing either strongly donating or withdrawing substituents are cleaved from triarylmethanols more readily than relatively neutral species.

Rate-limiting step of the Rh-catalyzed carboacylation of alkenes: C-C bond activation or migratory insertion?

Rhodium-catalyzed intramolecular carboacylation of alkenes, achieved using quinolinyl ketones containing tethered alkenes, proceeds via the activation and functionalization of a carbon-carbon single bond. This transformation has been demonstrated using RhCl(PPh(3))(3) and [Rh(C(2)H(4))(2)Cl](2) catalysts. Mechanistic investigations of these systems, including determination of the rate law and kinetic isotope effects, were utilized to identify a change in mechanism with substrate. With each catalyst, the transformation occurs via rate-limiting carbon-carbon bond activation for species with minimal alkene substitution, but alkene insertion becomes rate-limiting for more sterically encumbered substrates. Hammett studies and analysis of a series of substituted analogues provide additional insight into the nature of these turnover-limiting elementary steps of catalysis and the relative energies of the carbon-carbon bond activation and alkene insertion steps.

Infrasonic gliding reflects a rising magma column at Mount Etna (Italy).

Infrasound is increasing applied as a tool to investigate magma dynamics at active volcanoes, especially at open-vent volcanoes, such as Mt. Etna (Italy), which are prodigious sources of infrasound. Harmonic infrasound signals have been used to constrain crater dimensions and track the movement of magma within the shallow plumbing system. This study interprets the remarkable systematic change in monotonic infrasound signals preceding a lava fountaining episode at Mt. Etna on 20 February 2021. We model the changing tones (0.7 to 3 Hz fundamental frequency) as a rise in the magma column from 172 ± 25 m below the crater rim to 78 ± 8 m over the course of 24 h. The infrasonic gliding disappears approximately 4 h before the onset of lava fountaining as the magma column approaches the flare of the crater and acoustic resonance is no longer supported. The featured 20 February event was just one of 52 lava fountain episodes that occurred at Mt. Etna over the course of 9 months in 2021 and was the only lava fountain episode where dramatic gliding was observed as a subsequent partial collapse of the crater prevented future resonance. The results presented here demonstrate that analysis of infrasonic gliding can be used to track the position of the magma free surface and hence may provide information on the processes taking place within the plumbing system before eruptive activity.

Rhodium-catalyzed acylation with quinolinyl ketones: carbon-carbon single bond activation as the turnover-limiting step of catalysis.

The rhodium-catalyzed intramolecular carboacylation of quinolinyl ketones serves as an ideal subject for the mechanistic study of carbon-carbon bond activation. Combined kinetic and NMR studies of this reaction allowed the identification of the catalytic resting state and determination of the rate law, (12)C/(13)C kinetic isotope effects, and activation parameters. These results have identified the activation of a ketone-arene carbon-carbon single bond as the turnover-limiting step of catalysis and provided quantitative detail into this process.

Nickel-mediated decarbonylative cross-coupling of phthalimides with in situ generated diorganozinc reagents.

The nickel-mediated cross-coupling of phthalimides with diorganozinc reagents proceeds via a decarbonylative process to produce ortho-substituted benzamides in high yields. In addition to tolerating diverse phthalimide functionality, including alkyl, aryl, and heteroatom containing substituents, this methodology proceeds smoothly with diorganozinc reagents prepared from aryl bromides and utilized without purification.

UAS-based tracking of the Santiaguito Lava Dome, Guatemala.

Imaging growing lava domes has remained a great challenge in volcanology due to their inaccessibility and the severe hazard of collapse or explosion. Changes in surface movement, temperature, or lava viscosity are considered crucial data for hazard assessments at active lava domes and thus valuable study targets. Here, we present results from a series of repeated survey flights with both optical and thermal cameras at the Caliente lava dome, part of the Santiaguito complex at Santa Maria volcano, Guatemala, using an Unoccupied Aircraft System (UAS) to create topography data and orthophotos of the lava dome. This enabled us to track pixel-offsets and delineate the 2D displacement field, strain components, extrusion rate, and apparent lava viscosity. We find that the lava dome displays motions on two separate timescales, (i) slow radial expansion and growth of the dome and (ii) a narrow and fast-moving lava extrusion. Both processes also produced distinctive fracture sets detectable with surface motion, and high strain zones associated with thermal anomalies. Our results highlight that motion patterns at lava domes control the structural and thermal architecture, and different timescales should be considered to better characterize surface motions during dome growth to improve the assessment of volcanic hazards.

Spectroscopic determination of hydrogenation rates and intermediates during carbonyl hydrogenation catalyzed by Shvo's hydroxycyclopentadienyl diruthenium hydride agrees with kinetic modeling based on independently measured rates of elementary reactions.

The catalytic hydrogenation of benzaldehyde and acetophenone with the Shvo hydrogenation catalysts were monitored by in situ IR spectroscopy in both toluene and THF. The disappearance of organic carbonyl compound and the concentrations of the ruthenium species present throughout the hydrogenation reaction were observed. The dependence of the hydrogenation rate on substrate, H2 pressure, total ruthenium concentration, and solvent were measured. In toluene, bridging diruthenium hydride 1 was the only observable ruthenium species until nearly all of the substrate was consumed. In THF, both 1 and some monoruthenium hydride 2 were observed during the course of the hydrogenation. A full kinetic model of the hydrogenation based on rate constants for individual steps in the catalysis was developed. This kinetic model simulates the rate of carbonyl compound hydrogenation and of the amounts of ruthenium species 1 and 2 present during hydrogenations.

Nickel-catalyzed reductive carboxylation of styrenes using CO2.

A nickel-catalyzed reductive carboxylation of styrenes using CO2 has been developed. The reaction proceeds under mild conditions using diethylzinc as the reductant. Preliminary data suggests the mechanism involves two discrete nickel-mediated catalytic cycles, the first involving a catalyzed hydrozincation of the alkene followed by a second, slower nickel-catalyzed carboxylation of the in situ formed organozinc reagent. Importantly, the catalyst system is very robust and will fixate CO2 in good yield even if exposed to only an equimolar amount introduced into the headspace above the reaction.

More than bystanders: the effect of olefins on transition-metal-catalyzed cross-coupling reactions.

Olefins and alkynes are ubiquitous in transition-metal catalysis, whether introduced by the substrate, the catalyst, or as an additive. Whereas the impact of metals and ligands is relatively well understood, the effects of olefins in these reactions are generally underappreciated, even though numerous examples of olefins influencing the outcome of a reaction, through increased activity, stability, or selectivity, have been reported. This Review provides an overview of the interaction of olefins with transition metals and documents examples of olefins influencing the outcome of catalytic reactions, in particular cross-coupling reactions. It should thus provide a basis for the improved understanding and further utilization of olefin and alkyne effects in transition-metal-catalyzed reactions.

Selective substituent transfer from mixed zinc reagents in Ni-catalyzed anhydride alkylation.

The use of mixed zinc reagents in Ni-catalyzed anhydride alkylation results in preferential transfer of substituents (Ph > Me > Et >> iPr approximately TMSCH2) for the ligands bipy, dppe, and iPrPHOX. Utilization of such mixed species allows the use of 0.55 equiv of the diorganozinc reagent, effectively transferring both desired substituents when used in conjunction with a suitable second zinc reagent.

Rhodium-Catalyzed Interconversion of Quinolinyl Ketones with Boronic Acids via C-C Bond Activation.

A rhodium-catalyzed cross-coupling of aryl and aliphatic quinolinyl ketones with boronic acids has been developed. Proceeding via quinoline-directed carbon-carbon σ bond activation, the transformation demonstrates tolerance of a range of functional groups on both the ketone and aryl boronic acid substrates, providing good to excellent yields of the new ketones, particularly those containing electron-withdrawing substituents. Catalyst reactivity is dependent on quinolinyl ketone substrates, with alkyl ketones requiring Rh(PPh3)3Cl instead of the more reactive [Rh(C2H4)2Cl]2. With the use of K2CO3 as an additive, methyl boronic acid is also a competent substrate, giving rise to an unprecedented methylation technique.

Chain mechanism for exchange of D2 with a ruthenium hydride.

The ruthenium hydride of (Ar(4)CpOH)Ru(CO)(2)H exchanges cleanly and rapidly with D(2) at room temperature to generate the ruthenium deuteride. A chain mechanism is proposed to explain the much more rapid exchange of RuH/D(2) than RuCO exchange with (13)CO.

Enantioselective cross-coupling of anhydrides with organozinc reagents: the controlled formation of carbon-carbon bonds through the nucleophilic interception of metalacycles.

The construction of carbon-carbon bonds, particularly with concomitant control of newly formed asymmetric centers, is of paramount importance for the development of synthetic routes to complex organic molecules. While cross-coupling reactions for the generation of sp(2) carbon centers are well established, similar methodology for the formation and control of sp(3)-hydridized carbon stereocenters is extremely limited. We suggest that the nucleophilic interception of metalacycles provides the means to achieve such a transformation, wherein the metal complex serves to activate electrophiles, facilitate nucleophile addition, and ultimately control stereochemistry. One means of accessing these intermediates is through the use of simple meso-carboxylic anhydrides, which upon reaction with transition metals readily generate the desired metalacycles. Interception of the metalacycle with an appropriate carbon-based nucleophile generates an enantioenriched ketoacid, the product of the asymmetric desymmetrization of achiral starting materials. Early successes with achiral nickel catalysts and organozinc reagents provided the foundations for our approach. Alkylation of both succinic and glutaric anhydrides proceeds with a wide range of organozinc nucleophiles, forming 1,4- and 1,5-ketoacids in excellent yields. This reaction manifold has been extensively examined with a detailed kinetic study and mechanistic investigations utilizing mixed zinc reagents and alkene directing groups. This work has highlighted a number of unusual phenomena, including rate-limiting reductive elimination to form an sp(3)-sp(2) carbon-carbon bond. Despite excellent results with the achiral system, to date, all efforts to render the nickel-catalyzed reaction asymmetric have been limited to modest success. Palladium and rhodium complexes, with the use of chiral P-P and P-N ligands, respectively, have been identified as competent catalysts for the enantioselective addition of organozinc reagents to anhydrides. The arylation of a series of succinic anhydrides with Ph2Zn can be achieved in greater than 95% enantioselectivity using a Pd/Josiphos catalyst. Rhodium catalysts have proven amenable for the incorporation of in situ formed organozinc reagents, nucleophiles traditionally troublesome in transition metal catalysis due to the deleterious effects of residual halide ions. Highly functionalized organozinc nucleophiles, including those containing indole and furan, participate in this chemistry to provide the corresponding 1,4- and 1,5-ketoacids in excellent yield with greater than 85% enantioselectivity. This metalacycle interception methodology is currently being expanded to the use of other systems, most notably the asymmetric [2 + 2 + 2] cycloaddition of alkenes, alkynes, and isocyanates. Ongoing studies promise the extension of existing methodology toward the development of modular, fully intermolecular three-component couplings in which both metalacycle formation and nucleophilic interception can be controlled. Ultimately, we envision the use of heterocumulenes in such methodology, providing a route to complex products utilizing CO2 as an inexpensive C1 feedstock.

Ligand-dependent catalytic cycle and role of styrene in nickel-catalyzed anhydride cross-coupling: evidence for turnover-limiting reductive elimination.

Results from a mechanistic study on the Ni(COD)2-bipy-catalyzed alkylation of anhydrides are consistent with turnover-limiting reductive elimination at high Et2Zn concentrations. While the presence of styrene does not affect the initial rate of alkylation, it appears to inhibit catalyst decomposition and provides higher product yield at long reaction times. In contrast, Ni(COD)2-iPrPHOX-catalyzed anhydride alkylation proceeds through two competing catalytic cycles differentiated by the presence of styrene. The presence of styrene in this system appears to accelerate rate-limiting oxidative addition and promotes the cycle which proceeds 4 times more rapidly and with much higher enantioselectivity than its styrene-lacking counterpart.

Isomerization and deuterium scrambling evidence for a change in the rate-limiting step during imine hydrogenation by Shvo's hydroxycyclopentadienyl ruthenium hydride.

Hydroxycyclopentadienyl ruthenium hydride 5 efficiently reduces imines below room temperature. Better donor substituents on nitrogen give rise to faster rates and a shift of the rate-determining step from hydrogen transfer to amine coordination. Reduction of electron-deficient N-benzilidenepentafluoroaniline (8) at 11 degrees C resulted in free amine and kinetic isotope effects of k(OH)/k(OD) = 1.61 +/- 0.08, k(RuH)/k(RuD) = 2.05 +/- 0.08, and k(RuHOH)/k(RuDOD) = 3.32 +/- 0.14, indicative of rate-limiting concerted hydrogen transfer, a mechanism analogous to that proposed for aldehyde and ketone reduction. Reduction of electron-rich N-alkyl-substituted imine, N-isopropyl-(4-methyl)benzilidene amine (9), was accompanied by facile imine isomerization and scrambling of deuterium labels from reduction with 5-RuDOH into the N-alkyl substituent of both the amine complex and into the recovered imine. Inverse equilibrium isotope effects were observed in the reduction of N-benzilidene-tert-butylamine (11) at -48 degrees C (k(OH)/k(OD) = 0.89 +/- 0.06, k(RuH)/k(RuD) = 0.64 +/- 0.05, and k(RuHOH)/k(RuDOD) = 0.56 +/- 0.05). These results are consistent with a mechanism involving reversible hydrogen transfer followed by rate-limiting amine coordination.