Search results for "PAL"
showing 10 items of 11479 documents
PdII-mediated integration of isocyanides and azide ions might proceed via formal 1,3-dipolar cycloaddition between RNC ligands and uncomplexed azide
2016
Reaction between equimolar amounts of trans-[PdCl(PPh3)2(CNR)][BF4] (R = t-Bu 1, Xyl 2) and diisopropylammonium azide 3 gives the tetrazolate trans-[PdCl(PPh3)2(N4t-Bu)] (67%, 4) or trans-[PdCl(PPh3)2(N4Xyl)] (72%, 5) complexes. 4 and 5 were characterized by elemental analyses (C, H, N), HRESI+-MS, 1H and 13C{1H} NMR spectroscopies. In addition, the structure of 4 was elucidated by a single-crystal X-ray diffraction. DFT calculations showed that the mechanism for the formal cycloaddition (CA) of N3− to trans-[PdCl(PH3)2(CNMe)]+ is stepwise. The process is both kinetically and thermodynamically favorable and occurs via the formation of an acyclic NNNCN-intermediate. The second step of the fo…
Catalytic Carbonylative Double Cyclization of 2-(3-Hydroxy-1-yn-1-yl)phenols in Ionic Liquids Leading to Furobenzofuranone Derivatives
2019
A catalytic carbonylative double cyclization method for the synthesis of furo[3,4-b]benzofuran-1(3H)-ones is reported. It is based on the reaction between readily available 2-(3-hydroxy-1-yn-1-yl)phenols, CO, and oxygen carried out in the presence of catalytic amounts of PdI2 (1 mol %) in conjunction with KI (20 mol %) and 2 equiv of diisopropylethylamine at 80 degrees C for 24 h under 30 atm of a 1:4 mixture of CO-air. Interestingly, the process was not selective when carried out in classical organic non-nucleophilic solvents (such as MeCN or DME), leading to a mixture of the benzofurofuranone derivative and the benzofuran ensuing from simple cycloisomerization, whereas it turned out chemo…
Kinetic and Electrochemical Studies of the Oxidative Addition of Demanding Organic Halides to Pd(0): the Efficiency of Polyphosphane Ligands in Low P…
2013
International audience; Oxidative addition (OA) of organic halides to palladium(0) species is a fundamental reaction step which initiates the C–C bond formation catalytic processes typical of Pd(0)/Pd(II) chemistry. The use of structurally congested polyphosphane ligands in palladium-catalyzed C–C bond formation has generated very high turnover numbers (TONs) in topical reactions such as Heck, Suzuki, Sonogashira couplings, and direct sp2C–H functionalization. Herein, the OA of aryl bromides to Pd(0) complexes stabilized by ferrocenylpolyphosphane ligands L1 (tetraphosphane), L2 (triphosphane), and L3 (diphosphane) is considered. The investigation of kinetic constants for the addition of Ph…
The [Pd(bipy)]2+ “merry-go-round”: Insights into the lability of the Pd–N bond
2009
Abstract Two tripods (1 and 2) featuring pyrimidinyl pendant arms have been synthesized from 5-(1H-pyrazol-3-yl)-pyrimidine (5) and 1,3,5-tribromomethylbenzene derivatives. Reaction with three equivalents of [Pd(bipy)](NO3)2 to form a macrotricycle closed by palladium coordination unexpectedly afforded the mononuclear species [Pd(1)(bipy)]2+ and [Pd(2)(bipy)]2+. These complexes show fluxional behavior on the 1H NMR timescale, the [Pd(bipy)]2+ fragment hopping between the pyrimidinyl coordinating moieties. The ΔGc‡’s estimated by the coalescence method are temperature independent, which means that ΔSc‡ = 0. This indicates that the “merry-go-round” process of [Pd(bipy)]2+ occurs intramolecula…
Supramolecular Assembly of Organophosphonate Diesters Using Paddle-Wheel Complexes: First Examples in Porphyrin Series
2014
The reactions of dicopper tetrapivalate complex Cu2(μ-OOC-t-Bu)4(NCMe)2 (1) with triphenylphosphine oxide and diethyl phosphite allow paddle-wheel (PW) copper(II) complexes with phosphorus-containing axial ligands (2, 3) to be obtained. When meso-bis(diethoxyphosphoryl)porphyrins 4M were employed in this ligand exchange reaction, a series of one-dimensional (1D) homo- and heterometallic coordination polymers 5M composed of PW subunits and organophosphonate diesters were prepared and characterized by means of single crystal X-ray analysis. Planar porphyrinate 4Pd and nonplanar metalloporphyrinates 4Cu and 4Ni proved to be appropriate molecular structural blocks for assembly of coordination p…
The Chemo- and Stereoselective Formation of Pallado- and Platinocryptophanes
2019
International audience
Annually resolved δ13Cshell chronologies of long-lived bivalve mollusks (Arctica islandica) reveal oceanic carbon dynamics in the temperate North Atl…
2011
Abstract The ability of the ocean to absorb carbon dioxide is likely to be adversely affected by recent climate change. However, relatively little is known about the spatiotemporal variability in the oceanic carbon cycle due to the lack of long-term, high-resolution dissolved inorganic carbon isotope ( δ 13 C DIC ) data, especially for the temperate North Atlantic, which is the major oceanic sink for anthropogenic CO 2 . Here, we report shell carbon isotope values ( δ 13 C shell ), a potential proxy for δ 13 C DIC , of old-grown specimens of the long-lived bivalve mollusk, Arctica islandica . This paper presents the first absolutely dated, annually resolved δ 13 C shell record from surface …
Intercomparison of Soil Moisture Retrieved from GNSS-R and from Passive L-Band Radiometry at the Valencia Anchor Station
2019
In this paper, the SOMOSTA (Soil Moisture Monitoring Station) experiment on the intercomparison of soil moisture monitoring from Global Navigation Satellite System Reflectometry (GNSS-R) signals and passive L-band microwave radiometer observations at the Valencia Anchor Station is introduced. The GNSS-R instrument has an up-looking antenna for receiving direct signals from satellites, and a dual-pol down-looking antenna for receiving LHCP (left-hand circular polarization) and RHCP (right-hand circular polarization) reflected signals from the soil surface. Data were collected from the three different antennas through the two channels of Oceanpal GNSS-R receiver and, in addition, calibration …
The 1430s: a cold period of extraordinary internal climate variability during the early Spörer Minimum with social and economic impacts in north-west…
2016
Changes in climate affected human societies throughout the last millennium. While European cold periods in the 17th and 18th century have been assessed in detail, earlier cold periods received much less attention due to sparse information available. New evidence from proxy archives, historical documentary sources and climate model simulations permit us to provide an interdisciplinary, systematic assessment of an exceptionally cold period in the 15th century. Our assessment includes the role of internal, unforced climate variability and external forcing in shaping extreme climatic conditions and the impacts on and responses of the medieval society in north-western and central Europe. Climate…
The global forest above-ground biomass pool for 2010 estimated from high-resolution satellite observations
2021
Funding Information: We are thankful to the GlobBiomass project team and Frank Martin Seifert (ESA) for valuable suggestions and stimulating scientific discussions. We are thankful to Takeo Tadono (JAXA EORC), Masato Hayashi, (JAXA EORC), Kazufumi Kobayashi (RESTEC), Åke Rosenqvist (soloEO), and Josef Kellndorfer (EBD) for support with the use and interpretation of the ALOS PALSAR mosaics. Support by the CCI Land Cover project team, in particular Sophie Bontemps (UCL), is greatly acknowledged. The help from Martin Jung (MPI-BGC) in feature selection and Ulrich Weber (MPI-BGC) for data processing for the GSV-to-AGB conversions is greatly acknowledged. Forest inventory data for the validation…