1,10-Phenanthroline, complexes with

Convenient reagents for incorporation of perfluoroalkyl groups in a molecule of pyridine are 1,10-phenanthroline-ligated (perfluoroalkyl) copper (I) complexes 274 [166], which were obtained by reaction of copper 1,10-phenanthroline complex with Ruppert reagent and its CaFs-analog. The 1,10-phenanthroline complex (274a) has been used in reaction with 3-iodopyridine (273) for synthesis 3-trifluoromethylpyridine (275) [167, 168] (Scheme 81). 

Many of the studies purporting to show nucleophilic attack upon co-ordinated heterocyclic ligands have been performed with complexes of 5-nitro-l,10-phenanthro-line, 8.20. Unfortunately, this ligand proves to be a less than optimal choice, as nitroalke-nes undergo facile reactions with nucleophiles and, in contrast to simple pyridines, the free ligand reacts with hydroxide ion. Hydroxide ion and other nucleophiles react with 8.20 at the 6-position to give the stabilised anion 8.21 (Fig. 8-20). It is almost certain that the majority of the reactions of 5-nitro-l,10-phenanthroline complexes with hydroxide... 

Electrophilic activation can occur by both metal coordination and hydrogen bonding, and it is common for enzymes to combine these effects. Less common are synthetic systems that combine these, but one particularly simple example is the use of the diaminophenanthroline-Cu(II) complex shown below. This compound accelerates the hydrolysis of 2, 3 -cAMP(cAMP = cyclic adenosine monophosphate) approximately 20,000-fold compared to a Cu-phenanthroline complex with the amino groups replaced by methyls. 

A chromium atom forms a neutral complex with carbon monoxide molecules and 1,10-phenanthroline molecules. The structure of the complex is ... 

Interestingly, the rate constants for Diels-Alder reaction of the ternary complexes with 3.9 are remarkably similar. Only with 2,2 -bipyridine and 1,10-phenanthroline as ligands, a significant change in reactivity is observed. It might well be that the inability of these complexes to adopt a planar geometry hampers the interaction between the copper ion and the dienophile, resulting in a decrease of the rate of the catalysed Diels-Alder reaction. 

Crystal stmctures of complexes of copper(II) with aromatic amine ligands and -amino acids " " and dipeptides" have been published. The stmctures of mixed ligand-copper complexes of L-tryptophan in combination with 1,10-phenanthroline and 2,2 -bipyridine and L-tyrosine in combination with 2,2 -bipyridine are shown in Figure 3.2. Note the subtle difference between the orientation of the indole ring in the two 1,10-phenanthroline complexes. The distance between the two... 

It has been discovered that styrene forms a linear alternating copolymer with carbon monoxide using palladium II—phenanthroline complexes. The polymers are syndiotactic and have a crystalline melting point - 280° C (59). Shell Oil Company is commercializing carbon monoxide a-olefin plastics based on this technology (60). 

It has been established, that both DN and Ibp form complex compounds with ions Eu(III), Sm(III), Tb(III) and Dy(III), possessing luminescent properties. The most intensive luminescence is observed for complex compounds with ion Tb(III). It has been shown, that complexation has place in low acidic and neutral water solutions at pH 6,4-7,0. From the data of luminescence intensity for the complex the ratio of component Tb Fig was established equal to 1 2 by the continuous variations method. Presence at a solution of organic bases 2,2 -bipyridil, (Bipy) and 1,10-phenanthroline (Phen) causes the analytical signal amplification up to 250 (75) times as a result of the Bipy (Phen) inclusion in inner coordination sphere and formation of different ligands complexes with component ratio Tb Fig Bipy (Phen) = 1 2 1. 

There are more examples of a second type in which the chirality of the metal center is the result of the coordination of polydentate ligands. The easiest case is that of octahedral complexes with at least two achiral bidentate ligands coordinated to the metal ion. The prototype complex with chirality exclusively at the metal site is the octahedral tris-diimine ruthenium complex [Ru(diimine)3 with diimine = bipyridine or phenanthroline. As shown in Fig. 2 such a complex can exist in two enantiomeric forms named A and A [6,7]. The bidentate ligands are achiral and the stereoisomery results from the hehcal chirality of the coordination and the propeller shape of the complex. The absolute configuration is related to the handness of the hehx formed by the hgands when rotated... 

A stopped flow technique coupled with spectrophotometric analysis of the iron (II) complex formed has been used to investigate - the reactions of some organic complexes of iron(III) with the ion Fe ". The iron(III) was complexed with 1,10-phenanthroline, various substituted 1,10-phenanthrolines (5-methyl-, 5-nitro-, 5-chloro-, 5-phenyl-, 5,6-dimethyl-, 4,7-diphenyl-, and 3,4,7,8-tetramethyl-) and 2,2 -dipyridine, 4,4 -dimethyl-2,2 -dipyridine, and 2,2, 2"-tripyridine. The wavelengths used for the analysis lay in the region 500-552 m/i. 

These are thermodynamically relatively weak oxidants (Table 18) and their action is relatively restricted, for example, to inorganic ions of moderate reducing power such as iodide, to polyfunctional organic compounds such as hydroxy-acids, and, in the cases of Ag(I) and Cu(II), to CO and H2. Fe(III) is particularly affected by hydrolysis and all these oxidants form complexes with suitable ligands. Cyanide ion and 1,10-phenanthroline form strong complexes with Fe(III) which greatly affect its behaviour. Tris-l,10-phenanthrolineiron(III) (ferriin) displays... 

Molecular Metal Complexes Compounds of this type do not form delocalized electronic bands in the sohd state, and their color is due to intramolecular electronic transitions. Many complexes of transition metals with organic ligands belong to this class. complexes with phenanthroline (red/colorless) and Ru + + with 2,2 -... 

Konig and others published in the 1970s an impressive series of studies on six-coordinate iron(II)-bis-phenanthroline complexes [160-164] for which they inferred 5=1 from thorough magnetic susceptibility and applied-field Mossbauer measurements. Criteria for the stabilization of the triplet ground state for six-coordinate compounds with tetragonal ( >4 ) and trigonal ( >3 ) symmetry were obtained from LFT analyses [163], The molecular structures, however, were not known because the materials could not be crystallized. 

In a continuation of their earlier work,1 Hathaway and co-workers investigated crystal structures, electronic properties, and structural pathways for a series of five-coordinate complexes with two 1,10-phenanthroline (phen) ligands and axial ligands [(phen)2CuCl]Y [Y BF4 -0.51120 (269), PF6-(270), CF3S03--H20 (271) or BPh4 (272)],243 [(phen)2Cu(H20)][Y]2... 

The treatment of gold(III) complexes with the rigid bidentate ligand phen allows the synthesis of pseudo-pentacoordinate gold(III) derivatives. This is the case of [Au(dmp)(phen)PPh3](BF4)2 (288) (dmp = 2-(dimethylaminomethyl)phenyl)1699 or [AuCl(C4Ph4)(phen)].16 2 The donor atoms of the phenanthroline ligand occupy one equatorial and the axial position of a square pyramid with distances 2.154(8)A and 2.627(10)A in (288). 

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