The iron chelating ability of hydroxamic acid polymers was studied as a function of the atomic chain spacing separating neighboring hydroxamic acid units. Two polymers were prepared, one having the hydroxamic acid group separated by 11 atoms and the other by three atoms. The iron binding of these polymers was compared with the model compound desferrioxamine B (DFO) and with a previously prepared polymer having a nine-atom spacing. Mole ratio plots indicated the following order of stability: DFO ≈ 11 atom > 9 atom > 3 atom. These results are in accordance with the picture derived from molecular models which shows that with a spacing of 11 atoms, three neighboring hydroxamic acids can fit the octahedral arrangement of the iron (III) complex without appreciable strain. Some strain is introduced when the spacing becomes only nine atoms, and with three atoms, complex formation between three neighboring groups becomes virtually impossible. 相似文献
The photophysical properties of closely-coupled, binuclear complexes formed by connecting two ruthenium(II) tris(2,2'-bipyridine) complexes via an alkynylene group differ significantly from those of the relevant mononuclear complex. In particular, the energy of the first triplet excited state is lowered relative to the parent complex, because of the presence of the alkynylene substituent, while the triplet lifetime is prolonged, in part, because of extended electron delocalization. We now report that the triplet lifetime is also affected by the nature of the spectator 2,2'-bipyridyl ligands. Thus, replacing the parent 2,2'-bipyridine ligands with the corresponding 4,4'-dinitro-substituted ligands serves to decrease the luminescence yield and lifetime. With the corresponding carboxylate ester, the luminescence yield and lifetime are increased. Perdeuteration of the parent 2,2'-bipyridine ligands also leads to a modest increase in the luminescence yield. Such observations are indicative of electronic coupling between the various metal-to-ligand, charge-transfer excited triplet states. Temperature dependence studies confirm that these excited states are closely spaced and thermally accessible at ambient temperature. For some of the binuclear complexes, the quantum yield for formation of the lowest-energy triplet state is significantly less than unity. 相似文献
Although the arsenic containing analogue of triptycene, 5,10--benzenoarsanthrene (E=As) was isolated some time ago [1] the related derivatives of antimony and bismuth are unknown. We now find that when 1,2-diiodotetrafluorobenzene is treated with methyllithium at -78/dg, to afford the little studied dilithiotetrafluorobenzene [2], and the appropriate metal chloride is added to the resulting solution, perfluorinated analogues of (E = As, Sb, or Bi) are obtained in good yield. These are stable volatile solids.相似文献
Changing the counteranion along the series Br, BF4, PF6, SbF6 in their ion-paired 2-pyridylmethyl imidazolium salts causes the kinetic reaction products with IrH5(PPh3)2 to switch from chelating N-heterocyclic carbenes (NHCs) having normal C2 (N path) to abnormal C5 binding (AN path). Computational work (DFT) suggests that the AN path involves C-H oxidative addition to Ir(III) to give Ir(V) with little anion dependence. The N path, in contrast, goes by heterolytic C-H activation with proton transfer to the adjacent hydride. The proton that is transferred is accompanied by the counteranion in an anion-coupled proton transfer, leading to an anion dependence of the N path, and therefore of the N/AN selectivity. The N path goes via Ir(III), not Ir(V), because the normal NHC is a much less strong donor ligand than the abnormal NHC. PGSE NMR experiments support the formation of ion-pair in both the reactants and the products. 19F,1H-HOESY NMR experiments indicate an ion-pair structure for the products that is consistent with the computational prediction (ONIOM(B3PW91/UFF)). 相似文献
Amides have been successfully used as precursors of imidoyl radicals for radical cyclisation. The amides have been converted to imidoyl selanides via reaction with phosgene to yield imidoyl chlorides followed by reaction with potassium phenylselanide. Imidoyl selanides were reacted with tributyltin hydride (Bu3SnH) as the radical mediator with triethylborane or AIBN as initiators to yield imidoyl radicals for cyclisation reactions. Imidoyl radicals have been cyclised onto alkenes to yield 2,3-substituted-indoles and -quinolines and also onto pyrroles and indoles to give bi- and tricyclic heteroarenes. 相似文献
In an effort to build effective photovoltaic cells based on porphyrin-functionalised polythiophenes we have focused on synthetic routes to three monomer types. By controlling the geometric structure of the monomer, oxidation of these materials should produce polymers with different architectural structures, and as a result, different opto-electronic properties. Employing Wittig protocols allowed access to monomers in which the porphyrin moiety is connected to the beta-position of the thiophene via an alkene linkage. In addition, monomers were constructed using porphyrin condensation methods to afford alpha-thiophene meso-substituted porphryins. Another set of monomers was also prepared via porphyrin condensation routes, but instead utilising beta-formylthiophenes. By utilising different formyloligothiophenes we were able to generate a series of monomers that can be used to control the loading of the porphyrin in the polythiophene matrix. 相似文献
The algebraic number of disc minimal surfaces spanning a wire in 3 is defined and shown to be equal to one.The author wishes to acknowledge the support of the NSF. 相似文献
A number of new hypoxanthine analogs have been prepared as substrate inhibitors of xanthine oxidase. Most noteworthy inhibitory new hypoxanthine analogs are 3-(m-tolyl)pyrazolo[1,5-a]pyrimidin-7-one ( 47 ), ID50 0.06 μM and 3-phenylpyrazolo[1,5-a]pyrimidin-7-one ( 46 ), ID50 0.40 μM. 5-(p-Chlorophenyl)pyrazolo[1,5-a]pyrimidin-7-one ( 63 ) and the corresponding 5-nitrophenyl derivative 64 exhibited an ID50 of 0.21 and 0.23 μM, respectively. 7-Phenylpyrazolo[1,5-a]-s-triazin-4-one ( 40 ) is shown to exhibit an ID50 of 0.047 μM. The structure-activity relationships of these new phenyl substituted hypoxanthine analogs are discussed and compared with the xanthine analogs 3-m-tolyl- and 3-phenyl-7-hydroxypyrazolo[1,5-a]pyrimidin-5-ones ( 90 ) and ( 91 ), previously reported from our laboratory to have ID50 of 0.025 and 0.038 μM, respectively. The presence of the phenyl and substitutedphenyl groups contribute directly to the substrate binding of these potent inhibitors. This work presents an updated study of structure-activity relationships and binding to xanthine oxidase. In view of the recent elucidation of the pterin cofactor and the proposed binding of this factor to the molybdenum ion in xanthine oxidase, a detailed mechanism of xanthine oxidase oxidation of hypoxanthine and xanthine is proposed. Three types of substrate binding are viewed for xanthine oxidase. The binding of xanthine to xanthine oxidase is termed Type I binding. The binding of hypoxanthine is termed Type II binding and the specific binding of alloxanthine is assigned as Type III binding. These three types of substrate binding are analyzed relative to the most potent compounds known to inhibit xanthine oxidase and these inhibitors have been classified as to the type of inhibitor binding most likely to be associated with specific enzyme inhibition. The structural requirements for each type of binding can be clearly seen to correlate with the inhibitory activity observed. The chemical syntheses of the new 3-phenyl- and 3-substituted phenylpyrazolo[1,5-a]pyrimidines with various substituents are reported. The syntheses of various 8-phenyl-2-substituted pyrazolo-[1,5-a]-s-triazines, certain s-triazolo[1,5-a]-s-triazines and s-triazolo[1,5-a]pyrimidine derivatives prepared in connection with the present study are also described. 相似文献
3‐(Phenylsulfonyl)benzo[a]heptalene‐2,4‐diols 1 can be desulfonylated with an excess of LiAlH4/MeLi?LiBr in boiling THF in good yields (Scheme 6). When the reaction is run with LiAlH4/MeLi, mainly the 3,3′‐disulfides 6 of the corresponding 2,4‐dihydroxybenzo[a]heptalene‐3‐thiols are formed after workup (Scheme 7). However, the best yields of desulfonylated products are obtained when the 2,4‐dimethoxy‐substituted benzo[a]heptalenes 2 are reduced with an excess of LiAlH4/TiCl4 at ?78→20° in THF (Scheme 10). Attempts to substitute the PhSO2 group of 2 with freshly prepared MeONa in boiling THF led to a highly selective ether cleavage of the 4‐MeO group, rather than to desulfonylation (Scheme 13). 相似文献
Syntheses are reported of new 4,4'-dialkyl-2,2'-bithiazole oligomers that have alkenoxy side chains that are capable of easy conversion to oligomers with functionalized side chains, e.g., terminally substituted hydroxy chains. The crystal structures of two representative oligomers (4,4',4' ',4' "-tetra-(2-propenoxymethyl)-2,2',5',5' ',2' ',2' "-quaterthiazole (3P2) and 4,4',4' ',4' "-tetra-(3-hydroxypropyloxymethyl)-2,2',5',5' ',2' ',2' "-quaterthiazole (3H2)) were determined; 3P2 crystallizes in a pi-stacked motif with two molecules per unit cell, whereas 3H2 forms pi-stacks that are linked with hydrogen bonds to form infinite two-dimensional sheets with one molecule per unit cell. A comparison of the UV-vis spectra of the compounds in solution and in the solid state provides unequivocal evidence for the presence of a Davydov splitting, W(D) approximately 0.2 eV, in solid 3P2. The spectra are interpreted in the framework of molecular exciton theory to extract a value of the intermolecular transfer integral, J approximately 0.2 eV, for a total exciton bandwidth of ca. 0.8 eV. Monte Carlo calculations were used to determine the density of states of the exciton band and the absorption and emission line shapes of the 0 <-- 0 transition. It is suggested that the "three-humped" absorption profile typical of partially crystalline, regioregular polymers is the "optical signature" of pi-stacking. 相似文献