Search results for "Orbital"
showing 10 items of 679 documents
On the Road to MM′X Polymers: Redox Properties of Heterometallic Ni···Pt Paddlewheel Complexes
2014
On the quest of heterometallic mixed-valence MM'X chains, we have prepared two stable discrete bimetallic compounds: the reduced (PPN)[ClNi(μ-OSCPh)4Pt] (PPN = bis(triphenylphosphine)iminium; OSCPh = benzothiocarboxylato) and the oxidized [(H2O)Ni(μ-OSCPh)4PtCl] species. The role of the aqua and chlorido axial ligands is crucial to facilitate oxidation of the {Ni(μ-OSCPh)4Pt} core. Experimental and theoretical analyses indicate that a NiPt-Cl/Cl-NiPt isomerization process occurs in the oxidized species. The electronic structure of the reduced system shows two unpaired electrons, one located in a d(x(2)-y(2)) orbital of the Ni(II) ion and a second in the antibonding d(z(2)-dz(2)) combination…
Diels–Alder reaction on perylenediimides: synthesis and theoretical study of core-expanded diimides
2019
A one-step reaction for the fusion of aromatic rings to one or both bay areas of perylenediimides using benzynes is presented. Yields as high as 70% for naphthoperylenendiimide 2 and 80% for dibenzocoronenediimide 3 are obtained. The reaction is also carried out using substituted benzynes, heteroaromatic benzynes and substituted perylenediimides. A combined experimental/theoretical approach, based on measuring redox and absorption/emission properties and performing density functional theory calculations, indicates that increasing the π-skeleton of PDIs transversally leads to significant and unexpected changes in the electronic, redox and optical properties. The observed trends are rationali…
Oxotris(oxalate)niobate(V): An oxalate delivery agent in the design of building blocks
2018
This work concerns the oxalate delivery process that occurs when using (NH4)3[NbO(C2O4)3]·6H2O as a suitable oxalate source in the synthesis of two compounds, [Cu(dmphen)(C2O4)(H2O)] (1) and [{Cu(dmphen)(CH3OH)}2(μ-C2O4)](ClO4)2 (2) (dmphen = 2,9-dimethyl-1,10-phenanthroline). {[Fe{HB(pz)3}(CN)2(μ-CN)]2[{Cu(dmphen)}2(μ-C2O4)]}∙xCH3OH (3) (2.0 ≤ x ≤ 2.4) was obtained by reacting 2 and PPh4[Fe{HB(pz)3}(CN)3]∙H2O [ = tetraphenylphosphonium and = tris(pyrazolyl)borate]. Crystal structures of 1–3 have been determined by single-crystal X-ray diffraction experiments: 1 is a mononuclear trigonal bipyramidal copper(II) species, 2 is a centrosymmetric oxalato-bridged dicopper(II) complex, and 3 consi…
Higher MLCT lifetime of carbene iron(ii) complexes by chelate ring expansion
2021
Combining strong σ-donating N-heterocyclic carbene ligands and π-accepting pyridine ligands with a high octahedricity in rigid iron(ii) complexes increases the 3MLCT lifetime from 0.15 ps in the prototypical [Fe(tpy)2]2+ complex to 9.2 ps in [Fe(dpmi)2]2+12+. The tripodal CNN ligand dpmi (di(pyridine-2-yl)(3-methylimidazol-2-yl)methane) forms six-membered chelate rings with the iron(ii) centre leading to close to 90° bite angles and enhanced iron-ligand orbital overlap.
A P-chirogenic β-aminophosphine synthesis by diastereoselective reaction of the α-metallated PAMP–borane complex with benzaldimine
2004
International audience; The diastereoselective synthesis of a P-chirogenic β-aminophosphine ligand with carbon–carbon bond formation of the ethano bridge in a 3:1 ratio via reaction of an α-metallated P-chirogenic phosphine borane with a benzaldimine is described. The diastereoselectivity is attributed to a transition state where the lithium cation chelates the phosphine borane carbanion and the nitrogen of the imine and the attack of the C@N occurs on the face opposite to the P–B bond, due to its interaction with the antibonding P–B bond. The major diastereoisomeric β-aminophosphine borane was then separated and decomplexed into the corresponding β-aminophosphine under neutral conditions a…
Three X-ray Flares Near Primary Eclipse of the RS CVn Binary XY UMa
2016
We report on an archival X-ray observation of the eclipsing RS CVn binary XY UMa ($\rm P_{orb}\approx$ 0.48d). In two $\emph{Chandra}$ ACIS observations spanning 200 ks and almost five orbital periods, three flares occurred. We find no evidence for eclipses in the X-ray flux. The flares took place around times of primary eclipse, with one flare occurring shortly ($<0.125\rm P_{orb}$) after a primary eclipse, and the other two happening shortly ($<0.05\rm P_{orb}$) before a primary eclipse. Two flares occurred within roughly one orbital period ($\Delta \phi\approx1.024\rm P_{orb}$) of each other. We analyze the light curve and spectra of the system, and investigate coronal length scales both…
Astrometric detection of a low-mass companion orbiting the star AB Doradus
1997
International audience; We report submilliarcsecond-precise astrometric measurements for the late-type star AB Doradus via a combination of VLBI (very long baseline interferometry) and HIPPARCOS data. Our astrometric analysis results in the precise determination of the kinematics of this star, which reveals an orbital motion readily explained as caused by gravitational interaction with a low-mass companion. From the portion of the reÑex orbit covered by our data and using a revised mass of the primary star (0.76 M _) derived from our new value of the parallax (66.3 mas \ n \ 67.2 mas), we Ðnd the dynamical mass of the newly discovered companion to be between 0.08 and 0.11 If accurate photom…
A Pluto-like radius and a high albedo for the dwarf planet Eris from an occultation
2011
The dwarf planet Eris is a trans-Neptunian object with an orbital eccentricity of 0.44, an inclination of 44 degrees and a surface composition very similar to that of Pluto. It resides at present at 95.7 astronomical units (1ĝ€‰au is the Earth-Sun distance) from Earth, near its aphelion and more than three times farther than Pluto. Owing to this great distance, measuring its size or detecting a putative atmosphere is difficult. Here we report the observation of a multi-chord stellar occultation by Eris on 6 November 2010 ut. The event is consistent with a spherical shape for Eris, with radius 1,163±6 kilometres, density 2.52±0.05 grams per cm 3 and a high visible geometric albedo,. No nitro…
Orbital forcing of tree-ring data
2012
Based on an analysis of maximum latewood density data from northern Scandinavia, along with published dendrochronological records, this study finds evidence that previous tree-ring-reliant reconstructions of large-scale near-surface air temperature underestimated long-term pre-industrial warmth during Medieval and Roman times. Solar insolation changes, resulting from long-term oscillations of orbital configurations1, are an important driver of Holocene climate2,3. The forcing is substantial over the past 2,000 years, up to four times as large as the 1.6 W m−2 net anthropogenic forcing since 1750 (ref. 4), but the trend varies considerably over time, space and with season5. Using numerous hi…
High-resolution clay mineralogy as a proxy for orbital tuning: example of the Hauterivian-Barremian transition in the Betic Cordillera (SE Spain).
2012
11 pages; International audience; The response of clay mineral assemblages to potential orbital forcing is tested in Mesozoic hemipelagic marl- limestone rhythmites of the Río Argos section (Betic Cordillera, Southeastern Spain). Along the section, marls are pervasively enriched in kaolinite and illite, whereas limestones are enriched in smectite-rich illite/smectite mixed-layers, suggesting that marl-limestone alternations are produced by cyclic high-frequency fluctuations of continental runoff. Spectral analyses show that clay mineral assemblages evolve accordingly to precession, obliquity and eccentricity cycles. Durations of ammonite zones are assessed at 535 kyr for the Late Hauterivia…