1,10-Phenanthroline , complex cation with

Phenanthroline (o-phenan-throline), complex cation with nickel(II), 5 193n., 195 1-Phenylbiguanide complexes with eobalt(III), 6 71 Phosphate glasses, 3 88 Phosphates, analysis of mixtures of soluble, 3 91... 

Mixed donor ligands. The complex [FeL3]Cl3 (L = acetylhydrazine) contains the ligand in its bidentate form, bonded via the carbonyl and primary amino-groups.Pyridine-2-carboxaldehyde and l,l,l-tris(aminoethyl)ethane react with Fe" via a template reaction to form [Fejlpyljltame) ], in which three molecules of carboxaldehyde have condensed with one molecule of triamine to produce (pyljltame). MeC(CH2N=CH-oc-py)3 the complex cation is octahedral. The complexes [FeL ] (L = l,10-phenanthroline-2-carboxamide, n = 1 or 2) have been isolated they are both six-co-ordinate. Very weak d-d bands have been identified in the spectra of complexes of ot-picolinic acid and quinaldic acid with Fe". ... 

The reaction of a 1,10-phenanthroline complex of iridium, [Ir(cod)-(phen)]+, with dioxygen in methanol solution has been studied (38). When the anion for this cationic complex is chloride, no anion-cation interaction occurs, and the iridium system remains four-coordinate. However, when either iodide or thiocyanate is present due to the addition of their sodium salts (or in the presence of added triphenylphos-phine when the anion is chloride), the iridium system becomes five-coordinate because of the interaction between I", SCN", or PPh3 and the iridium center. These five-coordinate systems react more rapidly with dioxygen than did the four-coordinate system at both normal and elevated pressures. An end-on oxidative addition of the dioxygen moiety, with displacement of the , SCN, or PPh3 ligands, was postulated. 

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. 

A recent development31 is the preparation of metal polymer complexes directly on the electrode via the electrochemically induced polymerization of the metal complex. Ruthenium(II) and osmium(II) complexes with ligands containing aromatic amines, e.g. 3- or 4-aminopyridine or 5-amino-1,10-phenanthroline, are electrochemically polymerized to yield a film of the metal polymer on the electrode surface. The polymerization involves free radicals, which are formed via the initial oxidation of the metal complex to a radical cation and subsequent reaction of the radical cation with a base to yield the free radical. 

In acetonitrile solution the luminescence of [Eu(H20)4(o i-P2Wi706i)]7 increases with the addition of 1,10-phenanthroline or 2,2-bipyridine and reaches a limiting value with a 2 1 ratio of the bidentate ligand to polyoxometalate complex, consistent with the replacement of the four aqua ligands of the Eu cation (Boglio et al., 2006). 

Rubpy is an often used shorthand for the well studied [Ru(bpy)3]2+ complex cation and is also used more loosely to refer to any Ru(D) polypyridyl complex with similar properties. As shown in Fig. 7, the three best studied members of the Rubpy family are the parent complex, [Ru(bpy)3]2+, the phenanthroline analogue, [Ru(phen)3]2+, and the bis terpy complex, [Ru(terpy)3]2+, which has less optimal photophysical properties but has a number of synthetic and stereochemical advantages. The synthe sis, stability and photophysics of Rubpy complexes has been reviewed many times17 54 57 and the highlights of these properties as related to artificial photosynthetic assemblies is summarized here. 

Hence, the first clearcut evidence for the involvement of enol radical cations in ketone oxidation reactions was provided by Henry [109] and Littler [110,112]. From kinetic results and product studies it was concluded that in the oxidation of cyclohexanone using the outer-sphere one-electron oxidants, tris-substituted 2,2 -bipyridyl or 1,10-phenanthroline complexes of iron(III) and ruthenium(III) or sodium hexachloroiridate(IV) (IrCI), the cyclohexenol radical cation (65" ) is formed, which rapidly deprotonates to the a-carbonyl radical 66. An upper limit for the deuterium isotope effect in the oxidation step (k /kjy < 2) suggests that electron transfer from the enol to the metal complex occurs prior to the loss of the proton [109]. In the reaction with the ruthenium(III) salt, four main products were formed 2-hydroxycyclohexanone (67), cyclohexenone, cyclopen tanecarboxylic acid and 1,2-cyclohexanedione, whereas oxidation with IrCl afforded 2-chlorocyclohexanone in almost quantitative yield. Similarly, enol radical cations can be invoked in the oxidation reactions of aliphatic ketones with the substitution inert dodecatungstocobaltate(III), CoW,20 o complex [169]. Unfortunately, these results have never been linked to the general concept of inversion of stability order of enol/ketone systems (Sect. 2) and thus have never received wide attention. 

The enantiotopic protons of the prochiral methyl groups in the iminium salt 36 exhibited distinct resonances in the presence of Eu(hfc)3 . As already discussed for achiral lanthanide S-drketonates, the system likely forms an ion pair between the organic cation and the species [Ln( S-dik)3X]. The spectrum of racemic 37, which as its bromide salt has been studied as an ionic liquid, exhibits nonequivalence in the presence of Eu(tfc)3 and Eu(hfc)3. No splitting of the resonance occurs in the presence of Eu(fod)3. In addition to the likely ion-pairing interaction of 37 with [Ln(/ -dik)3X] , rather substantial shifts of some of the OCH2 protons implied that the ether oxygen atoms also likely coordinated with the europium ion. A similar ion-paired system explains the enantiomeric discrimination observed in the spectrum of the tris(phenanthroline) complexes of Ru(II) ([Ru(phen)3]Cl2) in the presence of Eu(tfc)3 . 

Mercury(II) forms with 1,10-phenanthroline a cationic complex which gives ion-associates with the acid dyes Rose Bengal B [57] and eosin [58] the associates have also been used for determining mercury in aqueous medium. 

REE ions with 1,10-phenanthroline form cationic complexes such as [La(phen)3 which give ion-associates with xanthene acid dyes, eosin or Erythrosin [117,118]. Molar absorptivities are of the order of 1-10. Europium(II) has been determined by an indirect method, after reduction of Fe(III) and reaction of the resulting Fe(II) with 1,10-phenanthroline [119]. 

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