Gallium-boron donor-acceptor bonds

Examples of compounds with gallium-boron donor-acceptor bonds, HC[MeC(2,6-pri2C6H3)N]2Ga-->B(C6F5)3 3 and (eta 5-C5Me5)Ga-->B(C6F5)3 4 have been prepared by treatment of the free gallanediyls with B(C6F5)3; the structures of both compounds were determined by X-ray crystallography.     

Base‐Stabilized Phosphinidene Boranes by Silylium‐Ion Abstraction

We report the preparation of N‐heterocyclic carbene (NHC)‐stabilized compounds containing P=B double bonds. The reaction of the highly functionalized phosphinoborane Mes*(SiMe₃)P?B(Cl)Cp* with Lewis bases allows access to base‐stabilized phosphinidene boranes Mes*P=B(L)Cp* (L=4‐dimethylaminopyridine (DMAP), NHC) by Me₃SiCl elimination. The formation of these species is shown to proceed through transient borylphosphide anions generated by Me₃Si abstraction.     

Numerical demonstration of fluctuation dynamo at low magnetic Prandtl numbers

Direct numerical simulations of incompressible nonhelical randomly forced MHD turbulence are used to demonstrate for the first time that the fluctuation dynamo exists in the limit of large magnetic Reynolds number Rm>1 and small magnetic Prandtl number Pm<1. The dependence of the critical Rmc for dynamo on the hydrodynamic Reynolds number Re is obtained for 1 less than or similar Re less than or similar 6700. In the limit Pm<1, Rmc is about 3 times larger than for the previously well-established dynamo at large and moderate Prandtl numbers: Rmc less than or similar 200 for Re greater than or similar 6000 compared to Rmc approximately 60 for Pm>or=1. It is not yet possible to determine numerically whether the growth rate of the magnetic energy is proportional, Rm1/2 in the limit Rm-->infinity, as it should be if the dynamo is driven by the inertial-range motions at the resistive scale.     

Characterization of the Zwitterionic Intermediate in 1,1‐Carboboration of Alkynes

The reaction of a Lewis acidic borane with an alkyne is a key step in a diverse range of main group transformations. Alkyne 1,1‐carboboration, the Wrackmeyer reaction, is an archetypal transformation of this kind. 1,1‐Carboboration has been proposed to proceed through a zwitterionic intermediate. We report the isolation and spectroscopic, structural and computational characterization of the zwitterionic intermediates generated by reaction of B(C₆F₅)₃ with alkynes. The stepwise reactivity of the zwitterion provides new mechanistic insight for 1,1‐carboboration and wider B(C₆F₅)₃ catalysis. Making use of intramolecular stabilization by a ferrocene substituent, we have characterized the zwitterionic intermediate in the solid state and diverted reactivity towards alkyne cyclotrimerization.     

Synthesis and Crystal Structure of a Decamethyleuropocene Complex Supported by a “Clamshell” Ligand

Abstract  

The coordination of decamethyleuropocene to a “clamshell” 1,2-bis(imino)acenaphthene (BIAN) ligand is accompanied by a one-electron redox process. The crystal structure of the Eu³⁺ product has been determined. The complex crystallizes in the triclinic space group P-1, with a = 12.065(2), b = 15.391(3), c = 17.266(4) ?, α = 73.71, β = 73.93(3), γ = 81.40(3)°, V = 2948.3(10) ?³ and Z = 2. The pyridine moiety of the clamshell ligand is not coordinated to the Eu³⁺ center.     

The bicritical phase diagram of two-dimensional antiferromagnets with and without random fields

Neutron scattering measurements have been made of the phase diagrams of the nearly two-demensional antiferromagnets Rb₂MnF₄ and Rb₂Mn_0.7Mg_0.3F₄ in a magnetic field applied along thec-axis. In Rb₂MnF₄ there is at low temperatures a spin-flop phase at fields above 5.5 T which has long range order. The observation of true long range order rather than the algebraic decay of the order characteristic of the two-dimensional XY model is presumably due to subtle anisotropy effects in the plane as well as weak three-dimensional coupling. The phase boundaries of the uniaxial and transverse phases are shown to be consistent with renormalization group predictions for two-dimensional systems. The two lines become exponentially close to each other at low temperatures. The weak three-dimensional coupling moves the bicritical point fromT=0 to a non-zero temperature. The situation is more complex in Rb₂Mn_0.7Mg_0.3F₄ because of Ising random field effects. At low fields we observe typical random field metastable behavior with a sharp metastability boundary and a gange of length scales which are time independent below that boundary. At higher fields there are substantial uniaxial fluctuations. The transverse phase boundary and the metastability line appear to intercept atT=0 showing that the random field fluctuations do have a large effect on the phase diagram. The theory of the phase diagrams has been extended to include the random field fluctuations and good agreement is obtained with the observed transverse phase boundary. Unfortunately, there is as yet no theory of the metastable uniaxial phase with which to compare our results.     

Surface imaging using diffracted electrons

Refection electron microscopy has been applied for studying single crystal surfaces of noble metals in a conventional electron microscope using diffracted electrons for the imaging. This is equivalent to dark field imaging in transmission electron microscopy. The image contains far more contrast due to deviation from the ideal surface structure than any other surface imaging technique. A resolution of the order of 20 Å has been achieved for directions perpendicular to the incident beam. In directions parallel to the incident beam the resolution is much worse and the magnification is reduced with a factor 15 to 100 because the surface is viewed at the angle of the diffracted beam used for imaging (foreshortening). Nevertheless the achieved resolution is one to two orders of magnitude better than for other surface imaging methods. Since a correspondence can be established between image and diffraction pattern by means of selected area diffraction, the present technique should be very useful in structure analysis of surfaces.     

A novel oxidative rearrangement of 6-methoxypyran-2-ones

As part of our continuing studies of pyrone-containing natural products, a series 6-methoxypyran-2-ones were synthesized. These were found to react with molecular oxygen at 20 degrees C, and this novel reaction yielded a series of highly functionalized alpha,beta-butenolides. [reaction: see text]     

Biomimetic synthesis of the pyrrolobenzoxazine core of paeciloxazine

Starting from a protected L-tryptophan derivative the pyrrolobenzoxazine core unit of paeciloxazine can be synthesized in two oxidation steps.     

Acetylacetonate bis(thiosemicarbazone) complexes of copper and nickel: towards new copper radiopharmaceuticals

A series of copper(II) and nickel(II) 1,3-bis(thiosemicarbazonato) complexes have been synthesised by the reaction of the metal acetates with pyrazoline proligands. In each case the complexes have an overall neutral charge with a dianionic ligand. The copper 1,3-bis(4-methyl-3-thiosemicarbazonato complex has been characterised by X-ray crystallography, which shows the copper is in an essentially square-planar symmetric N(2)S(2) environment. The nickel 1,3-bis(4-methyl-3-thiosemicarbazonato) and nickel 1,3-bis(4-phenyl-3-thiosemicarbazonato) complexes have been characterised by X-ray crystallography and show that in these cases the nickel is in a distorted square-planar environment, but the bonding mode of the ligands is unusual; the nickel binds to one of the aza-methinic nitrogen atoms and one hydrazinic nitrogen, creating one five-membered N-N-C-S-Ni chelate ring and one four-membered N-C-S-Ni chelate ring. Interestingly, the X-ray structure of the ethyl analogue [1,3-bis(4-ethyl-3-thiosemicarbazonato)nickel(II)] shows that in this case the nickel is symmetrically coordinated in the usual manner. The nickel complexes are diamagnetic and the different coordination modes are confirmed in solution by NMR spectroscopy. The complexes are susceptible to oxidation in air and a nickel complex, in which the central methylene carbon has been oxidised, has been characterised by X-ray crystallography and NMR spectroscopy. Electrochemical measurements show that the copper complexes undergo a reversible one-electron reduction at biologically accessible potentials.