The electrochemistry of cephalosporin C derivatives: Part II. Cephalothin,sodium salt

The electrochemical behavior of cephalothin has been studied by a.c. and d.c. polarography, cyclic voltammetry, and coulometry in both aqueous and nonaqueous media in order to gain a greater understanding of the reaction pathways involved in cephalosporin reduction. The reductive allylic cleavage of the 3′-acetoxy function has been found to produce Δ³-deacetoxy and 3-exomethylene cephalothin compounds (geometric isomers) and stereochemical isomers of the 3′-exomethylene compound at the 4-position. The ratio of these compounds to one another is dependent on the experimental conditions used, with adsorption playing an important role. The reductive allylic cleavage of the S₁?C₂ bond is a competitive reaction pathway. Δ³-Deacetoxy cephalothin may undergo further reduction, depending on the electrolysis potential selected.     

Metal-directed self-assembly of bimetallic dithiocarbamate transition metal cryptands and their binding capabilities

A novel family of redox-active dinuclear transition metal based cryptands self-assembled from dithiocarbamate ligands has been synthesised; depending upon the nature of the spacer groups these new cryptand systems have been shown to electrochemically recognise the binding of cations or anions.     

Knotted Zeros in the Quantum States of Hydrogen

Complex superpositions of degenerate hydrogen wavefunctions for the n th energy level can possess zero lines (phase singularities) in the form of knots and links. A recipe is given for constructing any torus knot. The simplest cases are constructed explicitly: the elementary link, requiring n6, and the trefoil knot, requiring n7. The knots are threaded by multistranded twisted chains of zeros. Some speculations about knots in general complex quantum energy eigenfunctions are presented.     

Investigation of active structural intensity control in finite beams: theory and experiment

An investigation of structural intensity control is presented in this paper. As opposed to previous work, the instantaneous intensity is completely taken into account in the control algorithm, i.e., all the terms are considered in the real-time control process and, in particular, the evanescent waves are considered in this approach. A finite difference approach using five accelerometers is used as the sensing scheme. A feedforward filtered-X least mean square algorithm is adapted to this energy-based control problem, involving a nonpositive definite quadratic form in general. In this respect, the approach is limited to cases where the geometry is such that the intensity component will have the same sign for the control source and the primary disturbance. Results from numerical simulations are first presented to illustrate the benefit of using a cost function based on structural intensity. Experimental validation of the approach is conducted on a free-free beam covered with viscoelastic material. A comparison is made between classical acceleration control and structural intensity control and the performance of both approaches is presented. These results confirm that using intensity control allows the error sensors to be placed closer to the control source and the primary disturbance, while preserving a good control performance.     

Analysis of electronically nonadiabatic chemical reactions: An information theoretic approach

A practical procedure for the determination of branching ratios for reactions which lead to either excited or electronically ground state products is outlined. The method is applied to four reactions which could (on energetic grounds) produce an electronically excited iodine atom. No case of a complete inversion is found, but one reaction (F + HI) is predicted to yield a statistical, (one half), I^*(²P_1/2) to I(²P_3/2) ratio.     

Iron-57 Mössbauer spectroscopy study of phases in the CaZrTi2−2x Nb x Fe x O7 zirconolite system

Materials of composition CaZrTi_2?2x Nb _x Fe _x O₇ with the fluorite-related zirconolite structure have been prepared. The ⁵⁷Fe Mössbauer spectra show that iron is initially located in the five co-ordinate cation sites. As the iron content increases the iron enters the octahedral sites until, at a composition CaZrTi_0.4Nb_0.8Fe_0.8O₇, ca. 50% of the iron is five co-ordinate and the remainder is located in the octahedral sites.     

High-resolution 17O NMR spectroscopy of wadsleyite (beta-Mg2SiO4)

The sensitivity of high-resolution 17O (I = 5/2) NMR spectroscopy of solids has advanced significantly in recent years. Here, we show that excellent results are now obtainable from milligram quantities of 17O-enriched materials, thereby allowing the technique to be applied to silicate phases synthesized under very high pressures in a multiple-anvil apparatus. We report the first 17O NMR study of beta-Mg2SiO4 (9.6 mg of 35% 17O-enriched material, synthesized at p = 16 GPa and T = 1873 K), a dense phase believed to have a significant role in the Earth's mantle. Using STMAS at magnetic fields of B0 = 9.4 and 11.7 T and MQMAS at B0 = 18.8 T, we have resolved and assigned all four crystallographically distinct O sites and determined their chemical shift and quadrupolar parameters.     

Jahn-Teller distortion,ferromagnetic coupling,and electron delocalization in a high-spin Fe–Fe bonded dimer

Fe₂(N,N’-diphenylformamidinate)₄, 1, first synthesized in 1994, is one of very few non-organometallic compounds with Fe–Fe distances, (2.46 Å) suggestive of an Fe–Fe bond. The electronic structure of 1 has been unclear because of its distorted D₂ geometry, as well as its reported S = 4 ground state. Computational investigations using DFT methods have shown that the D₂ geometry is the result of a Jahn-Teller distortion away from D₄ symmetry, in which the ground state would be orbitally degenerate. Broken symmetry methods have shown that ferromagnetic coupling between the two high-spin Fe(II) ions in 1 is a consequence of spin delocalization caused by a three-electron σ bond and a weaker three-electron δ bond between the Fe atoms. The relationship between ferromagnetic coupling and an Fe–Fe bond is established from results using hybrid functionals having variable amounts of Hartree-Fock exchange, which is found, surprisingly, to mitigate Fe–Fe bonding.     

Synthesis and reactivity of silyl ruthenium complexes: the importance of trans effects in C-H activation,Si-C bond formation,and dehydrogenative coupling of silanes

A series of octahedral ruthenium silyl hydride complexes, cis-(PMe(3))(4)Ru(SiR(3))H (SiR(3) = SiMe(3), 1a; SiMe(2)CH(2)SiMe(3), 1b; SiEt(3), 1c; SiMe(2)H, 1d), has been synthesized by the reaction of hydrosilanes with (PMe(3))(3)Ru(eta(2)-CH(2)PMe(2))H (5), cis-(PMe(3))(4)RuMe(2) (6), or (PMe(3))(4)RuH(2) (9). Reaction with 6 proceeds via an intermediate product, cis-(PMe(3))(4)Ru(SiR(3))Me (SiR(3) = SiMe(3), 7a; SiMe(2)CH(2)SiMe(3), 7b). Alternatively, 1 and 7 have been synthesized via a fast hydrosilane exchange with another cis-(PMe(3))(4)Ru(SiR(3))H or cis-(PMe(3))(4)Ru(SiR(3))Me, which occurs at a rate approaching the NMR time scale. Compounds 1a, 1b, 1d, and 7a adopt octahedral geometries in solution and the solid state with mutually cis silyl and hydride (or silyl and methyl) ligands. The longest Ru-P distance within a complex is always trans to Si, reflecting the strong trans influence of silicon. The aptitude of phosphine dissociation in these complexes has been probed in reactions of 1a, 1c, and 7a with PMe(3)-d(9) and CO. The dissociation is regioselective in the position trans to a silyl ligand (trans effect of Si), and the rate approaches the NMR time scale. A slower secondary process introduces PMe(3)-d(9) and CO in the other octahedral positions, most likely via nondissociative isomerization. The trans effect and trans influence in 7a are so strong that an equilibrium concentration of dissociated phosphine is detectable (approximately 5%) in solution of pure 7a. Compounds 1a-c also react with dihydrogen via regioselective dissociation of phosphine from the site trans to Si, but the final product, fac-(PMe(3))(3)Ru(SiR(3))H(3) (SiR(3) = SiMe(3), 4a; SiMe(2)CH(2)SiMe(3), 4b; SiEt(3), 4c), features hydrides cis to Si. Alternatively, 4a-c have been synthesized by photolysis of (PMe(3))(4)RuH(2) in the presence of a hydrosilane or by exchange of fac-(PMe(3))(3)Ru(SiR(3))H(3) with another HSiR(3). The reverse manifold - HH elimination from 4a and trapping with PMe(3) or PMe(3)-d(9) - is also regioselective (1a-d(9)() is predominantly produced with PMe(3)-d(9) trans to Si), but is very unfavorable. At 70 degrees C, a slower but irreversible SiH elimination also occurs and furnishes (PMe(3))(4)RuH(2). The structure of 4a exhibits a tetrahedral P(3)Si environment around the metal with the three hydrides adjacent to silicon and capping the P(2)Si faces. Although strong Si...HRu interactions are not indicated in the structure or by IR, the HSi distances (2.13-2.23(5) A) suggest some degree of nonclassical SiH bonding in the H(3)SiR(3) fragment. Thermolysis of 1a in C(6)D(6) at 45-55 degrees C leads to an intermolecular CD activation of C(6)D(6). Extensive H/D exchange into the hydride, SiMe(3), and PMe(3) ligands is observed, followed by much slower formation of cis-(PMe(3))(4)Ru(D)(Ph-d(5)). In an even slower intramolecular CH activation process, (PMe(3))(3)Ru(eta(2)-CH(2)PMe(2))H (5) is also produced. The structure of intermediates, mechanisms, and aptitudes for PMe(3) dissociation and addition/elimination of H-H, Si-H, C-Si, and C-H bonds in these systems are discussed with a special emphasis on the trans effect and trans influence of silicon and ramifications for SiC coupling catalysis.