Search results for "405"
showing 10 items of 3208 documents
Phospholylmethano P-chirogenic-phosphine-borane as P-(η2-BH3)-chelating ligands of rhodium (I): Synthesis, characterization and asymmetric hydrogenat…
2021
International audience; The stereoselective synthesis of new phospholylmethano P-chirogenic-phosphine-borane was achieved by P-C bond formation of the bridge, using electrophilic or nucleophilic P*-building blocks. These P1CH2P2*.BH3 ligands behaved as chelating (κ1-P1)-(η2-BH3) entities towards the cationic rhodium(I) centre. The resulting chiral rhodium complexes were tested in asymmetric rhodium catalyzed hydrogenation of methyl 2-(acetamido)acrylate.
Magneto-structural correlations and DFT calculations in two rare tetranuclear copper(II)-clusters with doubly phenoxo and end-on azido bridges: Synth…
2010
International audience; By slightly changing the synthetic conditions, we have prepared two closely related linear tetranuclear CuII complexes with the symmetrical ONNO donor tetradentate Schiff-base ligand [H2L = (OH)C6H4(CH3)Cdouble bond; length as m-dashN(CH2)3Ndouble bond; length as m-dashC(CH3)C6H4(OH)] and with azide ions. These two distinctly coloured crystalline products were characterized by elemental analysis, IR and UV–Vis spectroscopy, CV, EPR spectra and variable temperature magnetic measurements. Single crystal X-ray diffraction studies of the green [Cu4(μ-L)2(μ1,1-N3)2(N3)2] (1) and the red [Cu4(μ-L)2(μ1,1-N3)2(N3)2(H2O)2] (2) crystals show that the coordination environment o…
Excited State N−H Tautomer Selectivity in the Singlet Energy Transfer of a Zinc(II)-Porphyrin-Truxene-Corrole Assembly
2017
International audience; An original corrole-containing polyad for S-1 energy transfer, in which one zinc(II)-porphyrin donor is linked to two free-base corrole acceptors by a truxene linker, is reported. This polyad exhibits a rapid zinc(II)-porphyrin*free-base corrole transfer (4.83x10(10)s(-1); 298K), even faster than the tautomerization in the excited state processes taking advantage of the good electronic communication provided by the truxene bridge. Importantly, the energy transfer process shows approximately 3-fold selectivity for one corrole N-H tautomer over the other even at low temperature (77K). This selectivity is due to the difference in the J-integral being effective in both t…
Through-bond versus through-space T1 energy transfers in organometallic compound-metalloporphyrin pigments
2009
The preparation and characterization of two d9−d9 M2-bonded Pt2(dppm)2(C≡CC6H4-M(P))2 complexes (where M = Zn or Pd, and P = diethylhexamethylporphyrin) were achieved. The central [Pt2(dppm)2(C≡CC6H4)2] organometallic unit appears to be an independent chromophore and is suspected to be luminescent at 77 K (in 2MeTHF) in the porphyrin-containing complexes, as this is the case for the unfunctionalized Pt2(dppm)2(C≡CPh)2 parent compound. However, when this spacer is connected (by a single C−C bond) to either M(P) (M = Zn, Pd), even in the absence of conjugation (as the computed dihedral angle between the C6H4 and porphyrin planes is ∼84.5°), total quenching of the luminescence of the [Pt2(dppm…
The Aluminyl Anion : A New Generation of Aluminium Nucleophile
2020
Trivalent aluminium compounds are well known for their reactivity as Lewis acids/electrophiles, a feature that is exploited in many pharmaceutical, industrial and laboratory-based reactions. Recently, a series of isolable aluminium(I) anions ('aluminyls') have been reported, which offer an alternative to this textbook description: these reagents behave as aluminium nucleophiles. This minireview covers the synthesis, structure and reactivity of aluminyl species reported to date, together with their associated metal complexes. The frontier orbitals of each of these species have been investigated using a common methodology to allow for a like-for-like comparison of their electronic structure a…
Modular Approach to 9-Monosubstituted Fluorene Derivatives Using Mo(V) Reagents.
2016
Oxidative coupling using molybdenum(V) reagents provides fast access to highly functionalized 9-monosubstituted fluorenes. This synthetic approach is highly modular, is high yielding, and tolerates a variety of labile moieties, e.g. amides or iodo groups. The established protocol leads to promising precursors for pharmacologically important analogues of melatonin.
Green-Light Activation of Push-Pull Ruthenium(II) Complexes.
2020
Abstract Synthesis, characterization, electrochemistry, and photophysics of homo‐ and heteroleptic ruthenium(II) complexes [Ru(cpmp)2]2+ (22+) and [Ru(cpmp)(ddpd)]2+ (32+) bearing the tridentate ligands 6,2’’‐carboxypyridyl‐2,2’‐methylamine‐pyridyl‐pyridine (cpmp) and N,N’‐dimethyl‐N,N’‐dipyridin‐2‐ylpyridine‐2,6‐diamine (ddpd) are reported. The complexes possess one (32+) or two (22+) electron‐deficient dipyridyl ketone fragments as electron‐accepting sites enabling intraligand charge transfer (ILCT), ligand‐to‐ligand charge transfer (LL'CT) and low‐energy metal‐to‐ligand charge transfer (MLCT) absorptions. The latter peak around 544 nm (green light). Complex 22+ shows 3MLCT phosphorescenc…
A Versatile Palladium/Triphosphane System for Direct Arylation of Heteroarenes with Chloroarenes at Low Catalyst Loading
2010
International audience; Put a ring on it: The use of an air-stable, robust palladium/tridentate phosphane catalyst in direct C[BOND]H and C[BOND]Cl activation reactions is reported (see scheme; DMAc=N,N-dimethylacetamide, TBAB=tetra-n-butylammonium bromide). Electron-rich, electron-poor, and polysubstituted furans (X=O), thiophenes (X=S), pyrroles (X=NR5), and thiazoles were arylated with chloroarenes in the presence of the catalyst.
Proximity Effect using a Nanocage Structure: Polyhedral Oligomeric Silsesquioxane-Imidazolium Tetrachloro- palladate Salt as a Precatalyst for the Su…
2016
A polyhedral oligomeric silsesquioxane-imidazolium tetrachloropalladate salt (POSS-Imi-PdCl4) was prepared by the reaction of a polyhedral oligomeric silsesquioxane-imidazolium chloride salt (POSS-Imi-Cl) with PdCl2 and used as a pre-catalyst for the Suzuki-Miyaura reaction in water at 100 °C at a low loading (0.08-0.16 mol %). Biphenyl compounds were isolated in high to excellent yields. A comparison of the POSS-based catalyst with the corresponding catalyst without the nanocage structure (i.e., 1-butyl-3-methylimidazolium tetrachloropalladate) highlighted the role of the POSS structure to reach higher yields in the Suzuki-Miyaura reaction. This result is ascribed to a proximity effect of …
Palladium-based catalytic systems for the synthesis of conjugated enynes by Sonogashira reactions and related alkynylations
2007
Conjugated alkynes are recurring building blocks in natural products, a wide range of industrial intermediates, pharmaceuticals and agrochemicals, and molecular materials for optics and electronics. The palladium-catalyzed cross-coupling between sp(2)-hybridized carbon atoms of aryl, heteroaryl, and vinyl halides with sp-hybridized carbon atoms of terminal acetylenes is one of the most important developments in the field of alkyne chemistry over the past 50 years. The seminal work of the 1970s has initiated an intense search for more general and reliable reaction conditions. The interest in the catalytic activation of demanding substrates, the need to minimize the consumption of depletive r…