Interactions of nitrosonium salts with crown ethers

Interactions of nitrosonium tetrafluoroborate and hexafluorophosphate with 18-crown-6, 15-crown-5, and 12-crown-4 in dichloromethane, acetonitrile, and nitromethane have been probed by a combination of proton magnetic resonance spectroscopy, infrared spectroscopy, and conductance measurements. The stoichiometrics of the crown ether-nitrosonium salt complexes were one mole of 18-crown-6 per mole of nitrosonium salt and two moles of 12-crown-4 per mole of nitrosonium salt in all solvents. For 15-crown-5, the one-to-one stoichiometry observed in acetonitrile and nitromethane changed to two moles of crown ether per mole of nitrosonium salt in dichloromethane. The nature of these complexes is discussed. Treatment of a solution of equimolar nitrosonium hexafluorophosphate and 18-crown-6 in dichloromethane with water produced hydronium hexafluorophosphate-18-crown-6 complex.     

New lariat ether carboxylic and hydroxamic acids: Synthesis and lanthanide ion complexation

Twenty-six new lariat ether carboxylic and hydroxamic acids based upon dibenzo-13-crown-4, dibenzo-14-crown-4, dibenzo-16-crown-5 and dibenzo-19-crown-6 ring systems are synthesized and the solid-state structure for a dibenzo-19-crown-6 lariat ether hydroxamic acid is determined. The efficiency and selectivity for lanthanide ion extraction into chloroform by these proton-ionizable lariat ethers is strongly influenced by the crown ether ring size, lipophilic group attachment site and identity of the acidic function. In general, the lariat ether hydroxamic acids were more efficient and selective lanthanide ion extractants than the corresponding lariat ether carboxylic acids. The ¹H nmr and ir binding studies indicate that both the macrocyclic polyether unit and the proton-ionizable group are involved in lanthanide ion complexation.     

Triphospha-Ferrocenes as Ligands. Crystal Structures of [Fe(η5-C5Me5)(η5-C2 TBu2P3)M(CO)5)], (M= Cr,MO, W) and the Novel ruthenium and Nickel Complexes [Fe(η5-C5Me5) (η5-C2 TBu2P3)Ru3(CO)9] and [Fe(η5-C5Me5)(η5-C2 tBu2P3)Ni(Co)2]2

Abstract

Syntheses and structures of penta- and hexaphosphorus analogues of ferrocene have been described recently¹. Unlike their simple ferrocene analogues, these complexes have further ligating potential towards other transition metal centres by virtue of the availability of the ring phosphorus lone-pair electrons that are not involved in the η⁵-coordination. We now describe the first examples of coordination compounds of the triphospha-ferrocene [Fe(η⁵-C₅Me₅) (η⁵-C₂ ^tBu₂P₃]. In the ruthenium complex [Fe(η⁵-C₅Me₅)(η⁵-C₂ ^tBu₂P₃) Ru₃(CO)₉] ² two adjacent phosphorus atoms of the η⁵-C₂ ^tBu₂P₃ ring are interlinked by a ruthenium carbonyl cluster in which all three ruthenium atoms interact with the phosphorus atoms. The tetrametallic nickel complex [Fe(η⁵-C₅Me₅)(η⁵-C₂ ^tBu₂P₃)Ni(CO)₂]₂ ³ represents the first example of intermolecular interlinkage of two phospha-ferrocene systems by two metal centres.     

Synthesis of a Calix[4]crown‐6 Cone Conformer‐Based Oligomer and its Metal Cation Extraction Abilities

A new calixcrown‐6 oligomer 5 was synthesized by reacting a 1,3‐distal di‐amino derivative of cone p‐tert‐butylcalix[4]crown‐6 with malonyl dichloride. Extraction studies with precursor monomers 2 and 3 and oligomer 5 showed differences in their metal cation extraction behavior and selectivity. Precursors monomers 2 and 3 were selective for Hg²⁺; whereas, oligomer 5 showed high affinity towards both alkali (Li⁺, Na⁺, K⁺, and Cs⁺) and heavy metal cations (Cu²⁺, Cd²⁺, Hg²⁺ and Pb²⁺).     

Metal ion complexation in acetonitrile by cone,di-ionised calix[4]arene-1,2-crown ethers with two pendant dansyl fluorophores

Four cone calix[4]arene-1,2-crown ethers each with two ionisable side arms containing dansyl groups are synthesised. The crown ether ring on the lower rim is varied from crown-4 to crown-5 with hydrogen or tert-butyl groups on the para position of the upper rim. Di(tetramethylammonium) salts of the di-ionised ligands are utilised for spectrofluorimetric titration experiments in MeCN. The influence of alkali metal, alkaline earth metal and selected transition and heavy metal (Co²⁺, Fe²⁺, Hg²⁺, Mn²⁺, Pb²⁺, Zn²⁺ and Fe³⁺) cations on the spectroscopic properties of the two dansyl groups linked to the lower rim of the conformationally locked, di-ionised calix[4]arene-1,2-crown ether frameworks is investigated by emission spectrophotometry. All of the metal cations induce red shifts in the emission spectra of the di-ionised ligands. The metal cations produce enhancement or quenching of the fluorescence emissions. Changes in the fluorescence emission as a function of the metal cation identity, the lower rim crown ether ring size and the absence or presence of upper rim tert-butyl groups are investigated.     

Metal ion separations with proton-ionizable crown ethers and their polymers

Abstract

Lipophilic crown ethers with pendent proton-ionizable groups are novel complexing agents for use in metal ion separations by solvent extraction. For a series of structurally related, lipophilic dibenzocrown ether carboxylic acids, the efficiency and selectivity of competitive alkali metal cation extraction for aqueous solution into chloroform is found to be strongly influenced by the crown ether ring size and the lipophilic group attachment site. Reaction of dibenzocrown ether carboxylic acids with formaldehyde in formic acid produces condensation polymers which possess both ion-exchange and cyclic polyether binding sites for metal ion complexation. These resins exhibit excellent exchange kinetics for competitive alkali metal cation sorption from aqueous solution and subsequent stripping and may be used in concentrator columns for the recovery of these metal ions from very dilute aqueous solution. Cation selectivity in the sorption and stripping steps is controlled by the structure of the crown ether monomer unit.     

Analysis of the quantum numbers J(PC) of the X(3872) particle

We present an analysis of angular distributions and correlations of the X(3872) particle in the exclusive decay mode X(3872)-->J/psipi+ pi- with J/psi-->mu+ mu-. We use 780 pb-1 of data from pp[over ] collisions at sqrt[s]=1.96 TeV collected with the CDF II detector at the Fermilab Tevatron. We derive constraints on spin, parity, and charge conjugation parity of the X(3872) particle by comparing measured angular distributions of the decay products with predictions for different J(PC) hypotheses. The assignments J(PC)=1++ and 2-+ are the only ones consistent with the data.     

Measurement of the top-quark mass in all-hadronic decays in pp collisions at CDF II

We present a measurement of the top-quark mass Mtop in the all-hadronic decay channel tt-->W+bW-b-->q1q2bq3q4b. The analysis is performed using 310 pb-1 of sqrt[s]=1.96 TeV pp[over ] collisions collected with the CDF II detector using a multijet trigger. The mass measurement is based on an event-by-event likelihood which depends on both the sample purity and the value of the top-quark mass, using 90 possible jet-to-parton assignments in the six-jet final state. The joint likelihood of 290 selected events yields a value of Mtop=177.1+/-4.9(stat)+/-4.7(syst) GeV/c2.