Iron, tris structure

Iron, trinitrato(dinitrogen tetroxide)-structure, 1,28 Iron, tris(acetylacetone)-electron recording system, 6,127 structure, 1, 65 Iron, tris(bipyridyl)-... 

Iron, tris(hexafluoroacetylacetone)-structure, 1,65 Iron, tris(oxalato)-chemical actinometer, 1,409 photoreduction, 1,471 relief-image-forming systems, 6,125 Iron, tris(l,10-phenanthroline)-absorptiometry, 1,549 racemization, 1,466 solid state, 1,467 structure, 1, 64 lron(III) chloride amino acid formation prebiotic systems, 6,871 Iron complexes acetonitrile. 4,1210 acetylacetone, 2,371 amidines... 

The first of the coprogens (fungal sideramines ) was reported in 1973. Neocoprogen I (280) and neocoprogen II (281) are linear tris-hydroxamate siderophores whose chelating groups are derived from A -hydroxy-A -acylated ornithines. Neocoprogen I is the first structurally established example of a irons tris-hydroxamate siderophore. Subsequent studies have dealt with... 

The mixed oxide Fc304 (tri-iron tetroxide) is a black solid, which occurs naturally as magnetite it is formed when iron(III) oxide is strongly heated, and its structure is effectively made up of oxide (O ) and iron(II) and iron(III) ions. 

In order to answer these questions as directly as possible we begin by looking at diffusive and displacive transformations in pure iron (once we understand how pure iron transforms we will have no problem in generalising to iron-carbon alloys). Now, as we saw in Chapter 2, iron has different crystal structures at different temperatures. Below 914°C the stable structure is b.c.c., but above 914°C it is f.c.c. If f.c.c. iron is cooled below 914°C the structure becomes thermodynamically unstable, and it tries to change back to b.c.c. This f.c.c. b.c.c. transformation usually takes place by a diffusive mechanism. But in exceptional conditions it can occur by a displacive mechanism instead. To understand how iron can transform displacively we must first look at the details of how it transforms by diffusion. 

Iron(II) complex of tris(N -tert-butylurea-ylato)-N-ethylene]aminato activates dioxygen at room temperature to afford an iron(III) complex containing a single terminal oxo ligand. X-ray structures show that the three urea molecules act as a tridentate N,N,N-hgand [52]. The tripodal ligand was also used to synthesise complexes of cobalt, iron or zinc with terminal hydroxo ligands (Scheme 8) [53]. 

The phenothiazines, chlorpromazine and promethazine, have been described as inhibitors of CCU-induced lipid peroxidation at relatively high concentrations in rat liver microsomes (Slater, 1968). Structural modifications of chlorpromazine were undertaken to try to increase antioxidant activity and maintain molecular lipophilicity. The 2-N-N-dimethyl ethanamine methanesulphonate-substituted phenothiazine (3) was found to be a potent inhibitor of iron-dependent lipid peroxidation. It was also found to block Cu -catalysed oxidation of LDL more effectively than probucol and to protect primary cultures of rat hippocampal neurons against hydrogen peroxide-induced toxicity in vitro (Yu et al., 1992). 

Fig. 4.3 Ranges of isomer shifts observed for Fe compounds relative to metallic iron at room temperature (adapted from [24] and complemented with recent data). The high values above 1.4-2 mm s were obtained from Co emission experiments with insulators like NaCl, MgO or Ti02 [25-28], which yielded complex multi-component spectra. However, the assignment of subspectra for Fe(I) to Fe(III) in different spin states has never been confirmed by applied-field measurements, or other means. More recent examples of structurally characterized molecular Fe (I)-diketiminate and tris(phosphino)borate complexes with three-coordinate iron show values around 0.45-0.57 mm s [29-31]. The usual low-spin state for Fe(IV) with 3d configuration is 5 = 1 for quasi-octahedral or tetrahedral coordination. The low-low-spin state with S = 0 is found for distorted trigonal-prismatic sites with three strong ligands [30, 32]. Occurs only in ferrates. There is only one example of a molecular iron(VI) complex it is six-coordinate and has spin S = 0 [33]...

X-ray powder diagrams obtained by the Guinier method show the tris (O-ethyl dithiocarbonato) complexes of chro-mium(III), indium(III), cobalt(III), iron(III), arsenic(III), and antimony(III) to be isomorphous. Carrai and Gottardi have determined the structure of the arsenic(III)18 and anti-mony(III)19 complexes. Crystallographic data for the cobalt(III) and chromium(III) ethylxanthate complexes are given by Derenzini20 and Franzini and Schiaffino,21 respectively. 

The effect of the amino acid spacer on iron(III) affinity was investigated using a series of enterobactin-mimic TRENCAM-based siderophores (82). While TRENCAM (17) has structural similarities to enterobactin, in that it is a tripodal tris-catechol iron-binding molecule, the addition of amino acid spacers to the TRENCAM frame (Fig. 10) increases the stability of the iron(III) complexes of the analogs in the order ofbAla (19)complex stability is attributed to the intramolecular interactions of the additional amino acid side chains that stabilize the iron-siderophore complex slightly. 

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