Synthesis and structures of gold perfluorophthalimido complexes

Compounds of the new tetrafluorophthalimido anion, [C(6)F(4)(CO)(2)N](-), are readily accessible by treatment of tetrafluorophthalimide with either LiNPr(i)(2) or mixtures of NEt(3) and Me(3)ECl (E = Si or Sn), to give C(6)F(4)(CO)(2)N-X (X = Li 3, SiMe(3)4, and SnMe(3)5). The reaction of the trimethylsilyl derivative 4 with AgF leads cleanly to the ion pair complex [Ag(NCMe)(2)][Ag(N(CO)(2)C(6)F(4))(2)] (6·2MeCN), which contains a linear [Ag{N(CO)(2)C(6)F(4)}(2)](-) anion and a tetracoordinate Ag(+) cation. Compound 6 reacts with iodine to give the N-iodo compound C(6)F(4)(CO)(2)NI 7, which crystallises as an acetonitrile adduct. Treatment of 6 with LAuCl affords LAu{N(CO)(2)C(6)F(4)} (L = Ph(3)P 8a, Cy(3)P 8b, or THT 9), whereas the reaction with AuCl in acetonitrile affords the heterobinuclear compound [Ag(MeCN)(2)][Au{N(CO)(2)C(6)F(4)}(2)]·MeCN (10·3MeCN). The tetrafluorophthalimido ligand is not readily displaced by donor ligands; however, the addition of B(C(6)F(5))(3)(Et(2)O) to a diethyl ether solution of 8a leads to the salt [Au(PPh(3))(2)][N{COB(C(6)F(5))(3)}(2)C(6)F(4))] 11. The analogous reaction of (THT)Au{N(CO)(2)C(6)F(4)} with B(C(6)F(5))(3) in toluene in the presence of excess norbornene (nb) gives [Au(nb)(3)][N{COB(C(6)F(5))(3)}(2)C(6)F(4))] 12. Compounds 11 and 12 contain a new non-coordinating phthalimido-bridged diborate anion with O-bonded boron atoms. The crystal structures of compounds 2-11 are reported.     

Observation of postsoliton expansion following laser propagation through an underdense plasma

The expansion of electromagnetic postsolitons emerging from the interaction of a 30 ps, 3×101? W?cm?2 laser pulse with an underdense deuterium plasma has been observed up to 100 ps after the pulse propagation, when large numbers of postsolitons were seen to remain in the plasma. The temporal evolution of the postsolitons has been accurately characterized with a high spatial and temporal resolution. The observed expansion is compared to analytical models and three-dimensional particle-in-cell results, revealing a polarization dependence of the postsoliton dynamics.     

Low-temperature spin diffusion in a highly ideal S=1/2 Heisenberg antiferromagnetic chain studied by muon spin relaxation

The organic radical-ion salt DEOCC-TCNQF4 contains linear chains of stacked molecules with significant Heisenberg antiferromagnet interactions along the chain and extremely weak interactions between the chains. Zero-field muSR has confirmed the absence of long-range magnetic order down to 20 mK and field-dependent muSR is found to be consistent with diffusive motion of the spin excitations. The anisotropic spin dynamics and the upper boundary for magnetic ordering temperature both indicate interchain magnetic coupling /J'/<7 mK. As the intrachain coupling J is 110 K, /J'/J/ is significantly less than 10(-4). This system therefore provides one of the most ideal examples of the one-dimensional S=1/2 Heisenberg antiferromagnet yet discovered.     

Rayleigh quotient algorithms for nonsymmetric matrix pencils

A classical Rayleigh-quotient iterative algorithm (known as “broken iteration”) for finding eigenvalues and eigenvectors is applied to semisimple regular matrix pencils A − λB. It is proved that cubic convergence is attained for eigenvalues and superlinear convergence of order three for eigenvectors. Also, each eigenvalue has a local basin of attraction. A closely related Newton algorithm is examined. Numerical examples are included. Dedicated to the memory of Gene H. Golub.     

Detection of formaldehyde using mid-infrared difference-frequency generation

3 (PPLN) is reported. Minimum detectable concentration of 30 ppb was achieved with a compact, portable room-temperature gas sensor configured for formaldehyde (H₂CO) detection. This sensitivity, coupled with high selectivity and long term stability, is sufficient for various environmental applications. Received: 29 September 1997     

The influences of carbon donor ligands on biomimetic multi-iron complexes for N2 reduction

The active site clusters of nitrogenase enzymes possess the only examples of carbides in biology. These are the only biological FeS clusters that are capable of reducing N₂ to NH₄⁺, implicating the central carbon and its interaction with Fe as important in the mechanism of N₂ reduction. This biological question motivates study of the influence of carbon donors on the electronic structure and reactivity of unsaturated, high-spin iron centers. Here, we present functional and structural models that test the impacts of carbon donors and sulfide donors in simpler iron compounds. We report the first example of a diiron complex that is bridged by an alkylidene and a sulfide, which serves as a high-fidelity structural and spectroscopic model of a two-iron portion of the active-site cluster (FeMoco) in the resting state of Mo-nitrogenase. The model complexes have antiferromagnetically coupled pairs of high-spin iron centers, and sulfur K-edge X-ray absorption spectroscopy shows comparable covalency of the sulfide for C and S bridged species. The sulfur-bridged compound does not interact with N₂ even upon reduction, but upon removal of the sulfide it becomes capable of reducing N₂ to NH₄⁺ with the addition of protons and electrons. This provides synthetic support for sulfide extrusion in the activation of nitrogenase cofactors.

High-spin diiron alkylidenes give insight into the electronic structure and functional relevance of carbon in the FeMoco active site of nitrogenase.     

Electron transfer reactivity of type zero Pseudomonas aeruginosa azurin

Type zero copper is a hard-ligand analogue of the classical type 1 or blue site in copper proteins that function as electron transfer (ET) agents in photosynthesis and other biological processes. The EPR spectroscopic features of type zero Cu(II) are very similar to those of blue copper, although lacking the deep blue color, due to the absence of thiolate ligation. We have measured the rates of intramolecular ET from the pulse radiolytically generated C3-C26 disulfide radical anion to the Cu(II) in both type zero C112D/M121L and type 2 C112D Pseudomonas aeruginosa azurins in pH 7.0 aqueous solutions between 8 and 45 °C. We also have obtained rate/temperature (10-30 °C) profiles for ET reactions between these mutants and the wild-type azurin. Analysis of the rates and activation parameters for both intramolecular and intermolecular ET reactions indicates that the type zero copper reorganization energy falls in a range (0.9-1.1 eV) slightly above that for type 1 (0.7-0.8 eV), but substantially smaller than that for type 2 (>2 eV), consistent with XAS and EXAFS data that reveal minimal type zero site reorientation during redox cycling.     

Navigating localized wave packets in phase space

The ability to localize and to steer Rydberg wave packets in phase space using tailored sequences of half-cycle pulses is demonstrated. Classical phase-space portraits are used to explain the method and to illustrate the level of control that can be achieved. This is confirmed experimentally by positioning a phase-space-localized wave packet at the center of a stable island or navigating it around its periphery. This work provides a valuable starting point for further engineering of electronic wave functions.     

Monoenergetic electronic beam production using dual collinear laser pulses

The production of monoenergetic electron beams by two copropagating ultrashort laser pulses is investigated both by experiment and using particle-in-cell simulations. By proper timing between guiding and driver pulses, a high-amplitude plasma wave is generated and sustained for longer than is possible with either of the laser pulses individually, due to plasma waveguiding of the driver by the guiding pulse. The growth of the plasma wave is inferred by the measurement of monoenergetic electron beams with low divergence that are not measured by using either of the pulses individually. This scheme can be easily implemented and may allow more control of the interaction than is available to the single pulse scheme.