Catalytic Transformations of Alkynes via Ruthenium Vinylidene and Allenylidene Intermediates

NOTICE: This is the peer reviewed version of the following book chapter: Varela J. A., González-Rodríguez C., Saá C. (2014). Catalytic Transformations of Alkynes via Ruthenium Vinylidene and Allenylidene Intermediates. In: Dixneuf P., Bruneau C. (eds) Ruthenium in Catalysis. Topics in Organometallic Chemistry, vol 48, pp. 237-287. Springer, Cham. [doi: 10.1007/3418_2014_81]. This article may be used for non-commercial purposes in accordance with Springer Verlag Terms and Conditions for self-archiving.Vinylidenes are high-energy tautomers of terminal alkynes and they can be stabilized by coordination with transition metals. The resulting metal-vinylidene species have interesting chemical properties that make their reactivity different to that of the free and metal π-coordinated alkynes: the carbon α to the metal is electrophilic whereas the β carbon is nucleophilic. Ruthenium is one of the most commonly used transition metals to stabilize vinylidenes and the resulting species can undergo a range of useful transformations. The most remarkable transformations are the regioselective anti-Markovnikov addition of different nucleophiles to catalytic ruthenium vinylidenes and the participation of the π system of catalytic ruthenium vinylidenes in pericyclic reactions. Ruthenium vinylidenes have also been employed as precatalysts in ring closing metathesis (RCM) or ring opening metathesis polymerization (ROMP). Allenylidenes could be considered as divalent radicals derived from allenes. In a similar way to vinylidenes, allenylidenes can be stabilized by coordination with transition metals and again ruthenium is one of the most widely used metals. Metalallenylidene complexes can be easily obtained from terminal propargylic alcohols by dehydration of the initially formed metal-hydroxyvinylidenes, in which the reactivity of these metal complexes is based on the electrophilic nature of Cα and Cγ, while Cβ is nucleophilic. Catalytic processes based on nucleophilic additions and pericyclic reactions involving the π system of ruthenium allenylidenes afford interesting new structures with high selectivity and atom economy

Geology and Physical Properties Investigations by the InSight Lander

Although not the prime focus of the InSight mission, the near-surface geology and physical properties investigations provide critical information for both placing the instruments (seismometer and heat flow probe with mole) on the surface and for understanding the nature of the shallow subsurface and its effect on recorded seismic waves. Two color cameras on the lander will obtain multiple stereo images of the surface and its interaction with the spacecraft. Images will be used to identify the geologic materials and features present, quantify their areal coverage, help determine the basic geologic evolution of the area, and provide ground truth for orbital remote sensing data. A radiometer will measure the hourly temperature of the surface in two spots, which will determine the thermal inertia of the surface materials present and their particle size and/or cohesion. Continuous measurements of wind speed and direction offer a unique opportunity to correlate dust devils and high winds with eolian changes imaged at the surface and to determine the threshold friction wind stress for grain motion on Mars. During the first two weeks after landing, these investigations will support the selection of instrument placement locations that are relatively smooth, flat, free of small rocks and load bearing. Soil mechanics parameters and elastic properties of near surface materials will be determined from mole penetration and thermal conductivity measurements from the surface to 3–5 m depth, the measurement of seismic waves during mole hammering, passive monitoring of seismic waves, and experiments with the arm and scoop of the lander (indentations, scraping and trenching). These investigations will determine and test the presence and mechanical properties of the expected 3–17 m thick fragmented regolith (and underlying fractured material) built up by impact and eolian processes on top of Hesperian lava flows and determine its seismic properties for the seismic investigation of Mars’ interior

Young or not so young? Constraining the thermal evolution of the Moon with a landed mission to Ina-D

We propose a rover or lander mission to the Irregular Mare Patch (IMP) Ina-D. This idea was originally put forward in 2020 in response to ESA's call for ideas on the use of a European Large Logistic Lander (EL3). The mission scenario is focussed and comparably straightforward to be implemented, yet could answer fundamental science questions related to some of the most enigmatic lunar surface features and the thermal evolution of the Moon

The InSight HP3 Penetrator (Mole) on Mars: Soil Properties Derived from the Penetration Attempts and Related Activities

International audienceAbstract The NASA InSight Lander on Mars includes the Heat Flow and Physical Properties Package HP 3 to measure the surface heat flow of the planet. The package uses temperature sensors that would have been brought to the target depth of 3–5 m by a small penetrator, nicknamed the mole. The mole requiring friction on its hull to balance remaining recoil from its hammer mechanism did not penetrate to the targeted depth. Instead, by precessing about a point midway along its hull, it carved a 7 cm deep and 5–6 cm wide pit and reached a depth of initially 31 cm. The root cause of the failure – as was determined through an extensive, almost two years long campaign – was a lack of friction in an unexpectedly thick cohesive duricrust. During the campaign – described in detail in this paper – the mole penetrated further aided by friction applied using the scoop at the end of the robotic Instrument Deployment Arm and by direct support by the latter. The mole tip finally reached a depth of about 37 cm, bringing the mole back-end 1–2 cm below the surface. It reversed its downward motion twice during attempts to provide friction through pressure on the regolith instead of directly with the scoop to the mole hull. The penetration record of the mole was used to infer mechanical soil parameters such as the penetration resistance of the duricrust of 0.3–0.7 MPa and a penetration resistance of a deeper layer ( $>30~\text{cm}$ > 30 cm depth) of $4.9\pm0.4~\text{MPa}$ 4.9 ± 0.4 MPa . Using the mole’s thermal sensors, thermal conductivity and diffusivity were measured. Applying cone penetration theory, the resistance of the duricrust was used to estimate a cohesion of the latter of 2–15 kPa depending on the internal friction angle of the duricrust. Pushing the scoop with its blade into the surface and chopping off a piece of duricrust provided another estimate of the cohesion of 5.8 kPa. The hammerings of the mole were recorded by the seismometer SEIS and the signals were used to derive P-wave and S-wave velocities representative of the topmost tens of cm of the regolith. Together with the density provided by a thermal conductivity and diffusivity measurement using the mole’s thermal sensors, the elastic moduli were calculated from the seismic velocities. Using empirical correlations from terrestrial soil studies between the shear modulus and cohesion, the previous cohesion estimates were found to be consistent with the elastic moduli. The combined data were used to derive a model of the regolith that has an about 20 cm thick duricrust underneath a 1 cm thick unconsolidated layer of sand mixed with dust and above another 10 cm of unconsolidated sand. Underneath the latter, a layer more resistant to penetration and possibly containing debris from a small impact crater is inferred. The thermal conductivity increases from 14 mW/m K to 34 mW/m K through the 1 cm sand/dust layer, keeps the latter value in the duricrust and the sand layer underneath and then increases to 64 mW/m K in the sand/gravel layer below