Oxophosphonium ions (R2P=O)+ are fascinating chemical intermediates related to the well‐known acylium cations (RC=O)+, and comprise a tricoordinate phosphorus(V) center with a phosphorus–oxygen ...double bond. Here, we report the synthesis of two oxophosphonium ions stabilized by bulky imidazolin‐2‐imine and imidazolin‐2‐olefin substituents attached to phosphorus. The novel species were characterized by NMR spectroscopy and single‐crystal X‐ray diffraction analysis, and the bonding situation was probed by DFT calculations. Determination of the acceptor number and the fluoride ion affinity revealed that the choice of the substituents has a strong influence on the electrophilicity of the phosphorus center. Additionally, the formation of Lewis base adducts with pyridine derivatives and the reactivity with isopropyl alcohol was explored.
Free at last! Two Lewis base free oxophosphonium ions have been synthesized and structurally characterized. The electrophilicity of the phosphorus center strongly depends on the choice of the π‐donating substituents at phosphorus.
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A variety of chemical transformations benefit from the use of strong electron‐donating ancillary ligands, such as alkylphosphines or N‐heterocyclic carbenes when electron‐rich metal centers are ...required. Herein, we describe a facile and highly modular access to monodentate and bidentate imidazolin‐2‐ylidenamino‐substituted phosphines. Evaluation of the phosphine’s electronic properties substantiate that the formal replacement of alkyl or aryl groups by imidazolin‐2‐ylidenamino groups dramatically enhance their donor ability beyond that of alkylphosphines and even N‐heterocyclic carbenes. The new phosphines have been coordinated onto palladium(II) centers, and the beneficial effect of the novel substitution patterns has been explored by using the corresponding complexes in the palladium‐catalyzed Suzuki–Miyaura cross‐coupling reaction of non‐activated aryl chloride substrates.
Upgrading phosphines: A conceptually new approach to a family of extremely electron‐rich phosphines is based on the use of imidazolin‐2‐ylidenamino groups directly attached to the phosphorus atom. The steric and electronic properties of the new ligands can be easily varied owing to the general and modular synthesis, which provides new prospects for phosphine ligands in catalysis.
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Context. Low-mass stars are currently the best targets when searching for rocky planets in the habitable zone of their host star. Over the last 13 yr, precise radial velocities measured with the ...HARPS spectrograph have identified over a dozen super-Earths and Earth-mass planets (msini ≤ 10M⊕) around M dwarfs, with a well-understood selection function. This well-defined sample provides information on their frequency of occurrence and on the distribution of their orbital parameters, and therefore already constrains our understanding of planetary formation. The subset of these low-mass planets that were found within the habitable zone of their host star also provide prized targets for future searches of atmospheric biomarkers. Aims: We are working to extend this planetary sample to lower masses and longer periods through dense and long-term monitoring of the radial velocity of a small M dwarf sample. Methods: We obtained large numbers of HARPS spectra for the M dwarfs GJ 3138, GJ 3323, GJ 273, GJ 628, and GJ 3293, from which we derived radial velocities (RVs) and spectroscopic activity indicators. We searched for variabilities, periodicities, Keplerian modulations, and correlations, and attribute the radial-velocity variations to combinations of planetary companions and stellar activity. Results: We detect 12 planets, 9 of which are new with masses ranging from 1.17 to 10.5 M⊕. These planets have relatively short orbital periods (P< 40 d), except for two that have periods of 217.6 and 257.8 days. Among these systems, GJ 273 harbor two planets with masses close to the Earth's. With a distance of only 3.8 parsec, GJ 273 is the second nearest known planetary system - after Proxima Centauri - with a planet orbiting the circumstellar habitable zone. Based on observations made with the HARPS instrument on the ESO 3.6 m telescope under the program IDs 180.C-0886(A), 183.C-0437(A), and 191.C-0873(A) at Cerro La Silla (Chile).Radial velocity data (full Tables A.1-A.5) are only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr ( 130.79.128.5 ) or via cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/602/A88
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Abstract
The ExoClock project is an inclusive, integrated, and interactive platform that was developed to monitor the ephemerides of the Ariel targets to increase the mission efficiency. The project ...makes the best use of all available resources, i.e., observations from ground telescopes, midtime values from the literature, and finally, observations from space instruments. Currently, the ExoClock network includes 280 participants with telescopes capable of observing 85% of the currently known Ariel candidate targets. This work includes the results of ∼1600 observations obtained up to 2020 December 31 from the ExoClock network. These data in combination with ∼2350 midtime values collected from the literature are used to update the ephemerides of 180 planets. The analysis shows that 40% of the updated ephemerides will have an impact on future scheduling as either they have a significantly improved precision or they have revealed biases in the old ephemerides. With the new observations, the observing coverage and rate for half of the planets in the sample has been doubled or more. Finally, from a population perspective, we identify that the differences in the 2028 predictions between the old and the new ephemerides have an STD that is double what is expected from Gaussian uncertainties. These findings have implications for planning future observations, where we will need to account for drifts potentially greater than the prediction uncertainties. The updated ephemerides are open and accessible to the wider exoplanet community both from our Open Science Framework repository and our website.
While the metathesis reaction between alkynes and carbonyl compounds is an important tool in organic synthesis, the reactivity of alkynes with isoelectronic main-group R2EO compounds is unexplored. ...Herein, we show that oxophosphonium ions, which are the isoelectronic phosphorus congeners to carbonyl compounds, undergo 2 + 2 cycloaddition reactions with different alkynes to generate 1,2-oxaphosphete ions, which were isolated and structurally characterized. The strained phosphorus–oxygen heterocycles open to the corresponding heterodiene structure at elevated temperature, which was used to generate six-membered phosphorus heterocycles via hetero Diels–Alder reactions. Insights into the influence of the substituents at the phosphorus center on the energy profile of the oxygen atom transfer reaction were obtained by quantum-chemical calculations.
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Aims: The bright M2.5 dwarf K2-18 (Ms = 0.36 M⊙, Rs = 0.41 R⊙) at 34 pc is known to host a transiting super-Earth-sized planet orbiting within the star's habitable zone; K2-18b. Given the superlative ...nature of this system for studying an exoplanetary atmosphere receiving similar levels of insolation as the Earth, we aim to characterize the planet's mass which is required to interpret atmospheric properties and infer the planet's bulk composition. Methods: We have obtained precision radial velocity measurements with the HARPS spectrograph. We then coupled those measurements with the K2 photometry to jointly model the observed radial velocity variation with planetary signals and a correlated stellar activity model based on Gaussian process regression. Results: We measured the mass of K2-18b to be 8.0 ± 1.9M⊕ with a bulk density of 3.3 ± 1.2 g/cm3 which may correspond to a predominantly rocky planet with a significant gaseous envelope or an ocean planet with a water mass fraction ≳50%. We also find strong evidence for a second, warm super-Earth K2-18c (mp,csinic = 7.5 ± 1.3 M⊕) at approximately nine days with a semi-major axis 2.4 times smaller than the transiting K2-18b. After re-analyzing the available light curves of K2-18 we conclude that K2-18c is not detected in transit and therefore likely has an orbit that is non-coplanar with the orbit of K2-18b although only a small mutual inclination is required for K2-18c to miss a transiting configuration; | Δi| 1-2°. A suite of dynamical integrations are performed to numerically confirm the system's dynamical stability. By varying the simulated orbital eccentricities of the two planets, dynamical stability constraints are used as an additional prior on each planet's eccentricity posterior from which we constrain eb < 0.43 and ec < 0.47 at the level of 99% confidence. Conclusions: The discovery of the inner planet K2-18c further emphasizes the prevalence of multi-planet systems around M dwarfs. The characterization of the density of K2-18b reveals that the planet likely has a thick gaseous envelope which, along with its proximity to the solar system, makes the K2-18 planetary system an interesting target for the atmospheric study of an exoplanet receiving Earth-like insolation. Table A.2 is also available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr ( 130.79.128.5 ) or via cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/608/A35
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We present the confirmation of a new sub-Neptune close to the transition between super-Earths and sub-Neptunes transiting the M2 dwarf TOI-269 (TIC 220 479 565,
V
= 14.4 mag,
J
= 10.9 mag,
R
⋆
= ...0.40
R
⊙
,
M
⋆
= 0.39
M
⊙
,
d
= 57 pc). The exoplanet candidate has been identified in multiple TESS sectors, and validated with high-precision spectroscopy from HARPS and ground-based photometric follow-up from ExTrA and LCO-CTIO. We determined mass, radius, and bulk density of the exoplanet by jointly modeling both photometry and radial velocities with
juliet
. The transiting exoplanet has an orbital period of
P
= 3.6977104 ± 0.0000037 days, a radius of 2.77 ± 0.12
R
⊕
, and a mass of 8.8 ± 1.4
M
⊕
. Since TOI-269 b lies among the best targets of its category for atmospheric characterization, it would be interesting to probe the atmosphere of this exoplanet with transmission spectroscopy in order to compare it to other sub-Neptunes. With an eccentricity
e
= 0.425
−0.086
+0.082
, TOI-269 b has one of the highest eccentricities of the exoplanets with periods less than 10 days. The star being likely a few Gyr old, this system does not appear to be dynamically young. We surmise TOI-269 b may have acquired its high eccentricity as it migrated inward through planet-planet interactions.
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Exoplanet surveys have shown that systems with multiple low-mass planets on compact orbits are common. Except for a few cases, however, the masses of these planets are generally unknown. At the very ...end of the main sequence, host stars have the lowest mass and hence offer the largest reflect motion for a given planet. In this context, we monitored the low-mass (0.13 M⊙) M dwarf YZ Cet (GJ 54.1, HIP 5643) intensively and obtained radial velocities and stellar-activity indicators derived from spectroscopy and photometry, respectively. We find strong evidence that it is orbited by at least three planets in compact orbits (POrb = 1.97, 3.06, 4.66 days), with the inner two near a 2:3 mean-motion resonance. The minimum masses are comparable to the mass of Earth (M sin I = 0.75 ± 0.13, 0.98 ± 0.14, and 1.14 ± 0.17 M⊕), and they are also the lowest masses measured by radial velocity so far. We note the possibility for a fourth planet with an even lower mass of M sin I = 0.472 ± 0.096 M⊕ at POrb = 1.04 days. An n-body dynamical model is used to place further constraints on the system parameters. At 3.6 parsecs, YZ Cet is the nearest multi-planet system detected to date. Based on observations made with the HARPS instrument on the ESO 3.6 m telescope under the program IDs 180.C-0886(A), 183.C-0437(A), and 191.C-0873(A) at Cerro La Silla (Chile).Radial velocity data (Table B.4) are only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr ( 130.79.128.5 ) or via cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/605/L11
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ABSTRACT
We present the characterization of an inner mini-Neptune in a 9.2292005 ± 0.0000063 d orbit and an outer mono-transiting sub-Saturn planet in a 95.50$^{+0.36}_{-0.25}$ d orbit around the ...moderately active, bright (mv = 8.9 mag) K5V star TOI-2134. Based on our analysis of five sectors of TESS data, we determine the radii of TOI-2134b and c to be 2.69 ± 0.16 R⊕ for the inner planet and 7.27 ± 0.42 R⊕ for the outer one. We acquired 111 radial-velocity (RV) spectra with HARPS-N and 108 RV spectra with SOPHIE. After careful periodogram analysis, we derive masses for both planets via Gaussian Process regression: 9.13$^{+0.78}_{-0.76}$ M⊕ for TOI-2134b and 41.89$^{+7.69}_{-7.83}$ M⊕ for TOI-2134c. We analysed the photometric and RV data first separately, then jointly. The inner planet is a mini-Neptune with density consistent with either a water-world or a rocky core planet with a low-mass H/He envelope. The outer planet has a bulk density similar to Saturn’s. The outer planet is derived to have a significant eccentricity of 0.67$^{+0.05}_{-0.06}$ from a combination of photometry and RVs. We compute the irradiation of TOI-2134c as 1.45 ± 0.10 times the bolometric flux received by Earth, positioning it for part of its orbit in the habitable zone of its system. We recommend further RV observations to fully constrain the orbit of TOI-2134c. With an expected Rossiter–McLaughlin (RM) effect amplitude of 7.2 ± 1.3 $\rm m\, s^{-1}$, we recommend TOI-2134c for follow-up RM analysis to study the spin–orbit architecture of the system. We calculate the Transmission Spectroscopy Metric, and both planets are suitable for bright-mode Near Infrared Camera (NIRCam) atmospheric characterization.
ABSTRACT
We announce the discovery of GPX-1 b, a transiting brown dwarf with a mass of 19.7 ± 1.6 MJup and a radius of 1.47 ± 0.10 RJup, the first substellar object discovered by the Galactic Plane ...eXoplanet (GPX) survey. The brown dwarf transits a moderately bright (V = 12.3 mag) fast-rotating F-type star with a projected rotational velocity $v\sin {\, i_*}=40\pm 10$ km s−1. We use the isochrone placement algorithm to characterize the host star, which has effective temperature 7000 ± 200 K, mass 1.68 ± 0.10 $\mathrm{\it M}_\odot$, radius 1.56 ± 0.10 $\mathrm{\it R}_\odot$, and approximate age $0.27_{-0.15}^{+0.09}$ Gyr. GPX-1 b has an orbital period of ∼1.75 d and a transit depth of 0.90 ± 0.03 per cent. We describe the GPX transit detection observations, subsequent photometric and speckle-interferometric follow-up observations, and SOPHIE spectroscopic measurements, which allowed us to establish the presence of a substellar object around the host star. GPX-1 was observed at 30-min integrations by TESS in Sector 18, but the data are affected by blending with a 3.4 mag brighter star 42 arcsec away. GPX-1 b is one of about two dozen transiting brown dwarfs known to date, with a mass close to the theoretical brown dwarf/gas giant planet mass transition boundary. Since GPX-1 is a moderately bright and fast-rotating star, it can be followed-up by the means of the Doppler tomography.