1.10- phenanthroline-5,6-diamine

Very similar studies were carried out with the dinuclear Fe° complex [Fe(phdia)(NCS)2]2phdia (phdia = 4,7-phenanthroline-5,6-diamine), which exhibits an almost complete two-step thermally induced ST with a plateau around 100 K in the XmT vs. T magnetization curve [38]. After rapidly cooling the sample from the plateau down to 4.2 K the Mossbauer spectrum was recorded at that temperature in applied magnetic field of 5 T. The analysis of the magnetically perturbed spectmm indicated that the plateau consisted mainly of [HS-LS] pairs. 

The synthetic strategy used for the construction of concave pyridine bislactams 3 (Scheme 1) can also be applied to other concave bases. When instead of a pyridine-2,6-dialdehyde 4, l,10-phenanthroline-2,9-dicarbaldehyde (9) was used in a metal ion template directed synthesis of macrocyclic diimines, after reduction, also macrocyclic 1,10-phenanthroline diamines 10 could be obtained in good yields. Here too, the crude diamines 10 were used in the next reaction step. Bridging of 10 with diacyl dichlorides 8 gave concave 1,10-phenanthroline bislactams 11. Scheme 2 summarizes the synthesis and lists the synthesized bimacrocycles 11 [18]. 

Ligand abbreviations bi = 2,2 -bi-2-imidazoline bt = 2,2 -bi-2-thiazoline bpy = 2,2 -bipyridine phen = 1,10-phenanthroline phy = l,10-phenanthroline-2-carbaldehyde phenylhydrazone bpp = 2,6-bis(pyrazol-3-yl)pyridine paptH = 2-(2-pyridylamino)-4-(2-pyridyl)thiazole 2-pic = 2-picolylamine L = macrocyclic ligand derived from condensation of 2,6-diacetylpyridine with 3,6-dioxaoctane-1,8-diamine Hjthpu = pyruvic acid thiosemicarbazone Hjthpx = pyridoxal thiosemicarbazone salen = dianion of W,iV -ethylenebis(salicylideneimine) H2fsa2en = dianion of fV,JV -ethylenebis(3-carboxysalicylaldimine). 

A rough estimate of the total amount of anionic surfactant present can be obtained by reacting the surfactant with a metal-containing material such as bis(ethylenene diamine) copper (II) [199,200,203], or o-phenanthroline-CuS04, extracting the complex into an organic solvent (209 MIBK), and determining the metal by atomic absorption. 

Another novel synthesis of phenazines was introduced by Vagg and co-workers <00JHC151>. The key step was the reaction of dicarboxylic acid 230 with various 1,2-diamines to give 231, 232, and 233. Each was a potential polydentate ligand capable of interacting with DNA via their extended phenanthroline or phenazine components. 

Mn2+, D.F.P.-ase is further activated by cysteine, histidine, thiolhistidine, and serine, histamine and 2 2 -dipyridyl. Reagents reacting with metal ions, SH groups and carbonyl groups inhibit D.F.P.-ase activity. Work is proceeding on the further elucidation of such mechanisms.1 In a somewhat similar connexion attention is called to the fact that the non-enzymic hydrolysis of D.F.P. is accelerated by heavy metals and their complexes, in particular by copper chelates of ethylene diamine, o-phenanthroline, 2 2 -dipyridyl and histidine.2... 

Since 1980 the interest in this reaction increased because enantiospecificity was introduced and much more valuable products could be made. A wide variety of ligands was tested, such as chiral dipyridines, phenanthrolines, diphosphines, aminoalcohols, bis-oxazolines, bis-oxazolines with a third donor atom in the centre, bis-thioureas, diamines, etc [33], In 1981 the highest e.e. reported was still only 20%. For many years the best results were obtained with chiral diimines and phenanthrolines but e.e. s were below 70% [34], Pfaltz introduced bis-oxazolines for this reaction and obtained e.e. s as high as 91% [35] in 1991. 

Mo111 halide complexes formed with chelating diazadienes or diamines (N—N) include [MoCl3(CNMe)(N—N)] species with aromatic chelates such as 1,10-phenanthroline or 2,2 -bipyridine, salts containing the cation ds-[MoCl2(N—N)2]+ have been isolated.20 Compounds of stoichiometry [MoX3L4] are known for X = Cl, Br L = RCN and X = Br L2 = 2,6-lutidine,ls but it is not clear whether these involve seven-coordinate Mo111. 

Modification of the [Co(CN)5]3 catalyst by addition of diamines has been reported to lead to higher catalytic activity in diene hydrogenation and a predominant 1,2-addition of hydrogen. Such systems are thought to contain the species [CoH(CN)3(diamine)]. Ethylenediamine, 2,2 -bipyridyl and 1,10-phenanthroline were the diamines used.57 58... 

When short, flexible diamine a was used as a subcomponent in helicate formation, as shown on the left side of Scheme 1.7, only one topological isomer of product was observed twisted macrocycle 5. This diamine is not long enough to loop around the phenanthroline to form a catenated structure [28]. 

The high catalytic activity of [C4H7NiD] [C4H7NiI2] complexes obtained by the reaction of equimolar quantities of (C4H7NiI)2 and diamines (D = ,butadiene polymerization may occur at a nickel atom substituted by two iodines. 

---