Synthesis, structure, and physical properties for a series of monomeric iron(III) hydroxo complexes with varying hydrogen-bond networks

Mononuclear iron(III) complexes with terminal hydroxo ligands are proposed to be important species in several metalloproteins, but they have been difficult to isolate in synthetic systems. Using a series of amidate/ureido tripodal ligands, we have prepared and characterized monomeric Fe (III)OH complexes with similar trigonal-bipyramidal primary coordination spheres. Three anionic nitrogen donors define the trigonal plane, and the hydroxo oxygen atom is trans to an apical amine nitrogen atom. The complexes have varied secondary coordination spheres that are defined by intramolecular hydrogen bonds between the Fe (III)OH unit and the urea NH groups. Structural trends were observed between the number of hydrogen bonds and the Fe-O hydroxo bond distances: the more intramolecular hydrogen bonds there were, the longer the Fe-O bond became. Spectroscopic trends were also found, including an increase in the energy of the O-H vibrations with a decrease in the number of hydrogen bonds. However, the Fe (III/II) reduction potentials were constant throughout the series ( approximately 2.0 V vs [Cp 2Fe] (0/+1)), which is ascribed to a balancing of the primary and secondary coordination-sphere effects.     

Line positions and line strengths for the 3<--0 electric quadrupole band of H2 1Sigmag +

Several rotational lines in the S and Q branches [including the previously unobserved Q(2) and Q(3) lines] of the 3-0 electric quadrupole band of H2 have been detected by cavity ring-down spectroscopy. Line strengths were measured at densities between 2.7x10(18) and 7.5x10(19) molecules cm-3 at room temperature. The observed line strengths in the S branch are consistent with earlier measurements, and systematically below theoretical calculations [relative differences of approximately 10% for the S(1),S(2), and S(3) lines, and nearly 30% for the S(0) line]. Line strength measurements for the Q branch range from 25% to 33% below theoretical calculations.     

Temperaturabhängigkeit der Gleichgewichtsspreitungsdrucke homologer Lezithine an der Grenzfläche n-Heptan/0,1 M NaCl

Ohne ZusammenfassungMit 1 Abbildung und 1 Tabelle     

A unified analysis for a class of long-step primal-dual path-following interior-point algorithms for semidefinite programming

We present a unified analysis for a class of long-step primal-dual path-following algorithms for semidefinite programming whose search directions are obtained through linearization of the symmetrized equation of the central pathH _P (XS) [PXSP ^–1 + (PXSP ^–1) ^T ]/2 = I, introduced by Zhang. At an iterate (X,S), we choose a scaling matrixP from the class of nonsingular matricesP such thatPXSP ^–1 is symmetric. This class of matrices includes the three well-known choices, namely:P = S ^1/2 andP = X ^–1/2 proposed by Monteiro, and the matrixP corresponding to the Nesterov—Todd direction. We show that within the class of algorithms studied in this paper, the one based on the Nesterov—Todd direction has the lowest possible iteration-complexity bound that can provably be derived from our analysis. More specifically, its iteration-complexity bound is of the same order as that of the corresponding long-step primal-dual path-following algorithm for linear programming introduced by Kojima, Mizuno and Yoshise. © 1998 The Mathematical Programming Society, Inc. Published by Elsevier Science B.V.Corresponding author.This author's research is supported in part by the National Science Foundation under grants INT-9600343 and CCR-9700448 and the Office of Naval Research under grant N00014-94-1-0340.This author's research was supported in part by DOE DE-FG02-93ER25171-A001.     

Preparation of iron amido complexes via putative Fe(IV) imido intermediates

The isolation and characterization of monomeric Fe(III) amido complexes with hybrid ureate/amidate ligands is described. An aryl azide serves as the source of the amido ligand in preparing the complexes from trigonal monopyramidal Fe(II) precursors. Aryl azides more commonly react with transition metal complexes by a two-electron oxidation process to yield imido complexes, suggesting that the Fe(III) amido complexes may be formed from high valent species by hydrogen atom abstraction from an external species. The mechanistic basis for formation of the amido complexes is investigated using substrates that readily donate hydrogen atoms. Results from these experiments suggest that the Fe(III) amido complexes are generated from Fe(IV) imido intermediates that can facilitate homolytic X-H bond cleavage. The Fe(III) amido complexes are high spin (S = 5/2) with a strong absorbance band at lambdamax approximately 600 nm and extinction coefficients between 2000 and 3000 M-1 cm-1. These complexes are hygroscopic, reacting with 1 equiv of water to produce the corresponding Fe(III)-OH complexes and p-toluidine.     

Wetting of InP by indium- and indium-tin melts

Orientation dependent wetting of InP substrates by In- and In_xSn_1−x melts saturated with InP was studied using the sessile drop method. The contact angle was found to depend on the substrate orientation as follows: It is shown that a tin admixture to the indium melt improves the wetting behaviour. Additional to the dependence on substrate orientation it was found an anisotropic wetting on all investigated faces.