An unexpected ethyl transfer reaction between Et2Zn and DI(t-Butyl)-glyoxaldiimine (t-BuDAB). Studies of the persistent [EtZn(t-BuDAB)] radical which is in equilibrium with its C---C coupled dimer

Whereas p-Tol₂Zn reacts with t-BuN=CHCH=N-t-Bu (t-BuDAB) to give a stable complex [p-Tol₂Zn(t-BuDAB)], Et₂Zn gives EtZ -(t-Bu) via intramolecular ethyl transfer in the unstable Et₂Zn(t-BuDAB) complex. In solution the stable persistent organozinc radical EtZn(t-BuDAB), which is formed in trace amounts in the Et₂Zn/t-BuDAB reaction, is in equilibrium with its stable C---C coupled dimer [EtZn-t-BuN=CH(t-BuN)CH]₂. The dimer can be prepared in quantitative yield by the reaction of (EtZnCl)₄ with K(t-BuDAB).     

An unstructured finite element model for incompressible two-phase flow based on a monolithic conservative level set method

We present a robust numerical method for solving incompressible, immiscible two-phase flows. The method extends both a monolithic phase conservative level set method with embedded redistancing and a semi-implicit high-order projection scheme for variable-density flows. The level set method can be initialized conveniently via a simple phase indicator field instead of a signed distance function (SDF). To process the indicator field into a SDF, we propose a new partial differential equation-based redistancing method. We also improve the monolithic level set scheme to provide more accuracy and robustness in full two-phase flow simulations. Specifically, we perform an extra step to ensure convergence to the signed distance level set function and simplify other aspects of the original scheme. Lastly, we introduce consistent artificial viscosity to stabilize the momentum equations in the context of the projection scheme. This stabilization is algebraic, has no tunable parameters and is suitable for unstructured meshes and arbitrary refinement levels. The overall methodology includes few numerical tuning parameters; however, for the wide range of problems that we solve, we identify only one parameter that strongly affects performance of the computational model and provide a value that provides accurate results across all the benchmarks presented. This methodology results in a robust, accurate, and efficient two-phase flow model, which is mass- and volume-conserving on unstructured meshes and has low user input requirements, making it attractive for real-world applications.     

Comparison of free and metal coordinated 1,4-disubstituted-1,4-diaza-1,3-butadienes : Crystal and molecular structures of 1,4-dicyclohexyl-1,4-diaza-1,3-butadiene and trans-[dichloro(triphenylphosphine)(1,4-di-tert-butyl- 1,4-diaza-1,3-butadiene)palladium(II)]

The crystal and molecular structures of c-Hex-DAB (c-hexyl-NC(H)C(H)N-c-hexyl; DAB = 1,4-diaza-1,3-butadiene) and of trans-[PdCl₂(PPh₃)(t-Bu-DAB)] are reported. Crystals of c-Hex-DAB are monoclinic with space group C_2/c and cell constants: a = 24.70(1), b = 4.660(2), c = 12.268(3)Å, β = 107.66(4)°, Z = 4. The molecule has a flat E-s-trans-E structure with bond lengths of 1.258(3)Å for the CN double bond and 1.457(3)Å for the central CC′ bond. These bond lengths and the NC-C′ angle of 120.8(2)° indicate that the C- and N-atoms are purely sp²-hybridized and that there is little or no conjugation within the central DAB skeleton. Crystals of trans-[PdCl₂(PPh₃)(t-Bu-DAB)] are triclinic with space group P-1 and cell constants: a = 17.122(3), b = 18.279(3), c = 10.008(5)Å, α = 96.77(2), β = 95.29(3), γ = 109.79(2). Z = 4. The t-Bu-DAB ligand is coordinated to the metal via one lone pair only. In this 2e; σ-N coordination mode the E-s-trans-E conformation of the free DAB-ligand is still present and the bonding distances within the DAB-ligand are hardly affected. [CN: 1.261(10)Å; CC′: 1.479(10)Å (mean).] The PdN-, NC- and central CC′-bond lengths are compared with those found in other metal -R-DAB complexes.     

Complexes with metal-carbon bonds,part IV(1). Binuclear diarylplatinum(III) complexes. Long-rangetrans-effect in platinum-platinum bonded compounds containing methyl and aryl groups

Summary The platinum-platinum bonded [PtR₂(OAc)L¹]₂ complexes (R = Ph, L¹ = Et₂S, n-Pr₂S; R =p-tolyl, L¹ = Et₂S), have been prepared by oxidising [PrR₂L¹ ]₂ with AgOAc or Tl(OAc)₃. The sulphide ligand is replaced by weak ligands to give [PtR₂(OAc)L²]₂ (L² = PhNH₂, 4-picoline, CI^–) whereas PEt₃ or P(OMe)₃ react to give Pt₂R₄(OAc)₂(PR₃)(R = Et, OMe). The methyl platinum analogues could also be prepared. Similar complexes Pt₂Me₄(O₂CCF₃)₂L³ (L³ = Et₂S₁ 4-picoline) were obtained by the reaction of Hg(O₂CCF₃)₂ with [PtMe₂(O₂CCF₃)L³]₂.³¹p,¹H and¹³C n.m.r. of the complexes are reported.     

Gd‐TEMDO: Design,Synthesis, and MRI Application

A simple Ugi tetrazole multicomponent reaction allows the synthesis of a novel macrocyclic cyclen derivative with four appendant tetrazole arms in just two steps in excellent yields. This ligand, called TEMDO, turns out to have a high complexation affinity with lanthanoid metals. Here we describe the design, synthesis, solid‐state structure, binding constant, and some MRI applications of the Gd‐TEMDO complex as the first example of a congeneric family of oligo‐amino tetrazoles.     

An internal surface reversed phase column for the effective removal of humic acid interferences in the trace analysis of mecoprop in soils with coupled-column RPLC-UV

In the development of a screening method for the determination of residues of mecoprop in soils involving coupled-column RPLC-UV (228 nm) the cleanup performance of a 5 μm GFF-II internal surface reversed phase (ISRP, Pinkerton) analytical column (50 × 4.6 mm I.D.) as a first column was investigated. In comparison to an analytical C18 column the ISRP column substantially improved the separation between acidic analyte and co-extracted humic substances. Under the selected coupled-column conditions soil extracts obtained after hydrolysis with an aqueous alkaline solution, acidifying and centrifugation could be analyzed directly allowing the determination of mecoprop in soils to a level of about 0.02 mg/kg. A rapid concentration step on a 100 mg C18 solid phase extraction (SPE) cartridge was adopted into the procedure providing a limit of detection (S/N = 3) of 0.01 mg/kg of mecoprop in soil. The method was validated by analyzing freshly spiked soil samples and samples with aged residues. In case of freshly spiked samples the overall recovery was 87% (n = 18, spiked level 0.02–8.0 mg/kg) with a repeatability of 6.8% and a reproducibility of 8.3%. No significant decrease of the recovery was observed for samples with aged residues (n = 15, spiked level 0.1 and 8.0 mg/kg) during a storage of 29 days in the refrigerator at about 4 °C; a storage of 67 days provided a mean recovery of 76% (n = 14, spiked level 8.0 mg/kg). Received: 4 May 1998 / Revised: 11 July 1998 / Accepted: 18 July 1998     

Predicting the Time at Which a Lévy Process Attains Its Ultimate Supremum

We consider the problem of finding a stopping time that minimises the L ¹-distance to θ, the time at which a Lévy process attains its ultimate supremum. This problem was studied in Du Toit and Peskir (Proc. Math. Control Theory Finance, pp. 95–112, 2008) for a Brownian motion with drift and a finite time horizon. We consider a general Lévy process and an infinite time horizon (only compound Poisson processes are excluded. Furthermore due to the infinite horizon the problem is interesting only when the Lévy process drifts to ?∞). Existing results allow us to rewrite the problem as a classic optimal stopping problem, i.e. with an adapted payoff process. We show the following. If θ has infinite mean there exists no stopping time with a finite L ¹-distance to θ, whereas if θ has finite mean it is either optimal to stop immediately or to stop when the process reflected in its supremum exceeds a positive level, depending on whether the median of the law of the ultimate supremum equals zero or is positive. Furthermore, pasting properties are derived. Finally, the result is made more explicit in terms of scale functions in the case when the Lévy process has no positive jumps.