Crystallization-induced asymmetric transformation of chiral-at-metal ruthenium(II) complexes bearing achiral ligands

Recently, we observed that the enantiopure Lambda form of the tributylammonium salt of the chiral anion tris[tetrachlorobenzene-1,2-bis(olato)]phosphate, also named Trisphat, was able to induce an efficient resolution of a Delta,Lambda racemic mixture of cis-[Ru(dmp)2(NCCH3)2](PF6)2 (dmp=2,9-dimethyl-1,10-phenanthroline) due to the spontaneous and selective precipitation of the heterochiral pair [Delta-Ru(dmp)2(CH3CN)2][Lambda-Trisphat]2. We report here that the combination of such a stereoselective precipitation process and irradiation results in the quantitative conversion of the initial [Ru(dmp)2(NCCH3)2]2+ racemate into only one of the two enantiomers. This is the first example in inorganic chemistry of an asymmetric transformation that leads to a chiral complex with no chiral ligand. Finally, three new racemic ruthenium bis(diimine) complexes, namely [Ru(dmp)2(NCCH3)Py](PF6)2 (Py=pyridine), [Ru(dmp)2(1,3-diaminopropane)](PF6)2, and [Ru(dmp)2(ethylenediamine)](PF6)2 were synthesized. For all of them, crystallization-induced asymmetric transformation proved to be an efficient way of obtaining the corresponding optically active chiral-at-metal complexes in high yields and with excellent stereoselectivities.     

Surface characterization by underpotential deposition: Lead on gold surfaces

The kinetics of chelation of Pb(II), Zn(II) and Cd(II) with the ligand EDTA have been followed at the realistic trace concentration level 10^?8–10^?7M for both reactants in sea water and model solutions of its major salinity components by differential pulse stripping voltammetry. In this manner the specific influences of the salinity components on the formation rate constants [having in sea water for PbEDTA the order of 3×10³ and for the EDTA chelates of Zn(II) and Cd(II) of 3×10² l M^?1 s^?1] could be determined. The measurements emphasize the pronounced specific influences of Ca(II) on the kinetics and course of the trace metal chelation in media where this alkaline earth ion is present in substantial excess to organic chelating agents. The experiments with EDTA are to be regarded as a close simulation of the chelation processes occurring for the trace metals studied by components with suitable chelation power of dissolved organic matter (DOM) in the sea and the resulting conclusions on the mechanism are thus of general significance.     

A Ruthenium(II)–Copper(II) Dyad for the Photocatalytic Oxygenation of Organic Substrates Mediated by Dioxygen Activation

Dioxygen activation by copper complexes is a valuable method to achieve oxidation reactions for sustainable chemistry. The development of a catalytic system requires regeneration of the Cu^I active redox state from Cu^II. This is usually achieved using extra reducers that can compete with the Cu^II(O₂) oxidizing species, causing a loss of efficiency. An alternative would consist of using a photosensitizer to control the reduction process. Association of a Ru^II photosensitizing subunit with a Cu^II pre‐catalytic moiety assembled within a unique entity is shown to fulfill these requirements. In presence of a sacrificial electron donor and light, electron transfer occurs from the Ru^II center to Cu^II. In presence of dioxygen, this dyad proved to be efficient for sulfide, phosphine, and alkene catalytic oxygenation. Mechanistic investigations gave evidence about a predominant ³O₂ activation pathway by the Cu^I moiety.     

Probing fission time scales with neutrons and GDR gamma rays

The time scales for nuclear fission have been explored using both pre-and postfission neutrons and GDR gamma rays. Four systems were investigated: 133-MeV ¹⁶O + ¹⁷⁶Yb and ²⁰⁸Pb and 104-MeV ⁴He + ¹⁸⁸Os and ²⁰⁹Bi. Fission fragments were measured in coincidence with PPACs. The neutrons were detected using eight detectors from the DEMON array, while gamma rays were measured using the US BaF2 array. The pre-and postfission gamma rays were determined using moving source fits parallel and perpendicular to the fission fragment emission directions. The time scales for fission for the neutrons were determined using the neutron clock technique. The gamma-ray data were fitted using a statistical model calculation based on the code CASCADE. The results of the fits from both data types were used to extract nuclear friction coefficients, γ, and fission time scales. The γ values ranged from 7 to 20, while the fission times were (31–105)×10^?21 s.     

Addition d'hydrazone aux oléfines en milieu acide: cycloaddition polaire cationique [3+ + 2]

The stereospecificity and the orientation observed for the addition reaction of acetaldehyde hydrazone with (E)- and (Z)-alkenes in acidic media are compatible with a concerted process of the polar [3⁺ + 2] cycloaddition type.     

Study of the (210) face of gold in aqueous solutions

Among all the gold faces studied to date, the (210) face has the most negative pzc and therefore should be less affected by preoxidation than the other faces. But the (210) gold face-sodium fluoride solution interface is ideally polarizable only in a short range of potential. Nevertheless, differential capacity-potential curves have been tentatively exploited. There seems to be adsorption of the fluoride ions on the (210) face of gold. The inner-layer capacity-charge curves are discussed.     

One‐pot synthesis of new 3‐substituted coumarins by tandem reactions

The synthesis of new 3‐substituted coumarins appended to imidazolium, pyridinium, 3‐dimethylamino pyridinium, 3‐chloro pyridinium and 3‐bromo pyridinium salts is reported. These salts were prepared by tandem reactions, followed by quantitative anionic metathesis. The structure of these new 3‐substituted coumarins was established by NMR (¹H, ¹³C) and high‐resolution mass spectrometry.     

Regioselective aza-annulation to a heterocyclic ketene aminal: A new route to ethyl 1-oxo-2,3-dihydropyrido-[1,2-a]-(5H)-perimidine-4-carboxylates

Ethyl (1H-perimidin-2-yl)acetate 1 reacts with various acrylic acid chlorides 3 to afford new ethyl 1-oxo-2,3-dihydropyrido-[1,2-a]-(5H)-perimidine-4-carboxylates 4 by regioselective aza-annulation with the appropriate base. The ¹H, ¹³C NMR spectrum of some representative annulated perimidines 4 and C_β-acylated products 7 are discussed. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:523–528, 1998