Double C-H activation during functionalization of phenyl(methyl)ketene on iridium(I) using alkynes. synthesis of 1,4-dien-3-ones

Under the influence of an Ir(I) metal fragment, the methyl group of phenyl(methyl)ketene undergoes two C-H activations in reacting with internal alkynes, giving metallacycles 3 in 86-94% yield. Treatment of 3 with CO liberates 1,4-dien-3-ones 5 in 81-93% yield, along with CO complex 4. A possible mechanism for the very selective double C-H activation-alkyne coupling is discussed.     

Fourier transform spectroscopy on the 3ν2, 2ν2 + ν6 and ν3 + ν5 bands of H2CO

Fourier transform spectra covering the range from 1500 to 5400 cm^?1 with 0.02-cm^?1 resolution have been obtained for formaldehyde. A study of the region above 4000 cm^?1 has yielded rotational constants and other asymmetric rotor parameters for three bands: 3ν₂ (ν₀ = 5177.7611 ± 0.0005 cm^?1)2ν₂ + ν₆ (ν₀ = 4734.193 ± 0.004 cm^?1), and ν₃ + ν₅ (ν₀ = 4335.102 ± 0.001 cm^?1). An analysis of the A-type Coriolis interaction between the 2ν₂ + ν₆ state and the unobserved 2ν₂ + ν₄ state has yielded partially deperturbed rotational constants for the 2ν₂ + ν₆ state. Vibration-rotation interaction constants have been obtained for the ν₂ and ν₆ normal modes by combining the present results with those of previous workers.     

Study of intrinsic localized vibrational modes in micromechanical oscillator arrays

Intrinsic localized modes (ILMs) have been observed in micromechanical cantilever arrays, and their creation, locking, interaction, and relaxation dynamics in the presence of a driver have been studied. The micromechanical array is fabricated in a 300 nm thick silicon-nitride film on a silicon substrate, and consists of up to 248 cantilevers of two alternating lengths. To observe the ILMs in this experimental system a line-shaped laser beam is focused on the 1D cantilever array, and the reflected beam is captured with a fast charge coupled device camera. The array is driven near its highest frequency mode with a piezoelectric transducer. Numerical simulations of the nonlinear Klein-Gordon lattice have been carried out to assist with the detailed interpretation of the experimental results. These include pinning and locking of the ILMs when the driver is on, collisions between ILMs, low frequency excitation modes of the locked ILMs and their relaxation behavior after the driver is turned off.     

Vancomycin assembly: nature's way

Antibiotics are precious resources in the fight to combat bacterial infections caused by pathogenic organisms. Vancomycin is one of the antibiotics of last resort in the treatment of life-threatening infections by gram-positive bacteria. The rules by which nature assembles the glycopeptide (vancomycin) and lipoglycopeptide (teicoplanin) antibiotics are becoming elucidated and verified: first amino acids are synthesized, then joined together and cross-linked. This knowledge opens up approaches for reprogramming strategies at the level of altered monomers, swapped assembly lines, and different post-assembly tailoring enzymes.     

First direct structural comparison of complexes of the same metal fragment to ketenes in both C,C- and C,O-bonding modes

Using a series of Ir(I) and Rh(I) ketene complexes, conclusions about the structure and bonding of complexes of the fundamentally important ketene ligand class are reached. In a unique comparison of X-ray structures of the same metal fragment to ketenes in both the eta(2)-(C,C) and the eta(2)-(C,O) binding mode, the Ir-Cl bond distances in complexes of trans-Cl(Ir)[P(i-Pr)(3)](2) to phenylketene [4, eta(2)-(C,C)] and diphenylketene [2a, eta(2)-(C,O)] are 2.371(3) and 2.285(2) A, respectively. This would be consistent with greater trans influence of a ketene ligand bound to a metal through its C=C bond than one connected by its C=O bond. Back-bonding of Ir(I) and Rh(I) to diphenylketene was assessed using trans-Cl(M)[P(i-Pr)(3)](2)[eta(2)-(C,O)-diphenylketene] (2a and 2d). Most bond lengths and angles are identical, but slightly greater back-bonding by Ir(I) is suggested by the somewhat greater deformation of the ketene C=C=O system [C-C-O angles are 136.6(4) and 138.9(4) in the Ir and Rh cases 2a and 2d, respectively]. Syntheses of new labeled ketenes Ph(2)C=(13)C=O and Ph(2)C=C=(18)O and their Ir(I) and Rh(I) complexes are reported, along with the generation of an Ir(I) complex of PhCH=(13)C=O. The effects of isotopic substitution on infrared absorption data for ketene complexes are presented for the first time. Preliminary normal coordinate mode analysis allowed definitive assignment of absorptions ascribed to the C-O stretching frequencies of coordinated ketenes, which are near the absorptions for aromatic ring systems commonly found as substituents on ketenes. For free diphenylketene and four of its complexes and a phenylketene complex characterized by X-ray diffraction, the magnitude of the (13)C-(13)C coupling between the two ketene carbons is correlated to carbon-carbon bond distance.     

Transverse modulation of an electron beam generated in self-modulated laser wakefield accelerator experiments

Low energy electron beams (E approximately 300 keV) generated in a self-modulated laser wakefield accelerator experiment were observed to filament and be deflected away from the laser axis forming radial jets in the electron beam profile. At higher energies (E>900 keV), the filamentation and jets were suppressed and smooth electron beams copropagating with the laser were observed. The observed electron beam filamentation likely results from laser beam filamentation in the plasma due to relativistic self-focusing effects. The radial jets of low energy electrons are likely caused by transverse ejection of the electrons due to the radial structure of the wakefield and space charge deflection of electrons as they exit the laser focus.     

Experimental observation of the bifurcation dynamics of an intrinsic localized mode in a driven 1D nonlinear lattice

Linear response spectra of a driven intrinsic localized mode in a micromechanical array are measured as it approaches two fundamentally different kinds of bifurcation points. A linear phase mode associated with this autoresonant state softens in frequency and its amplitude grows as the upper frequency bifurcation point is approached, similar to the soft-mode kinetic transition for a single driven Duffing resonator. A lower frequency bifurcation point occurs when the four-wave-mixing partner of this same phase mode intercepts the top of the extended wave branch, initiating a second kinetic transition process.