Metal complexes of 1,10-phenanthrolines

What happens if we look at the K2 or Ki, values for didentate ligands In general, the Kj values show stability patterns which closely parallel those for K. However, the values are different. Figure 8-17 presents K, data for transition-metal complexes of 1,10-phenanthroline and 1,2-diaminoethane (Eq. 8.14). 

McBryde, W. A. E. A Critical Review of Equilibrium Data for Proton- and Metal Complexes of 1,10-Phenanthroline, 2,2-Bipyridyl and Related Compounds Pergamon Oxford, 1978. 

The products of the thermal decomposition of 1,10-phenanthroline have been briefly discussed.370 Exchange of hydrogen for deuterium has been noted with alkali metal complexes of 1,10-phenanthroline. The exchange occurs principally in the 5-position.371,372 A new chemiluminescence reaction arising from the combination of trichloroacetic acid and 4,7-diphenyl-l,10-phenanthroline has been reported.373... 

There are many examples of the analytical use of 1,10-phenanthroline and its derivatives in biological systems by virtue of their chelating properties. Uses that depend solely on these properties are outside the scope of this review. The biological effects of metal complexes of 1,10-phenanthroline are also excluded. These have been reviewed.394... 

McKenzie, E. D. (1962) A physico-chemical study of transition metal complexes of 1,10-phenanthroline and related ligands. Ph. D. Thesis, University of New South Wales. 

Sigman DS, Landgraf R, Perrin DM, Pearson L (1996) Nucleic acid chemistry of the cuprous complexes of 1,10-phenanthroline and derivatives. In Sigel A, Siegel H (eds) Probing of nucleic acids by metal ion complexes metal ions in biological systems Vol. 33. Marcel Dekker, New York, pp 485-513... 

Other detection methods have been used in optical MIP sensing systems. An MIP-based chemiluminescent flow-through sensor was developed for the detection of 1,10-phenanthroline (Lin and Yamada 2001). A metal complex was used to catalyze the decomposition of hydrogen peroxide and form the superoxide radical ion that can... 

The importance of 1,10-phenanthroline and substituted 1,10-phenanthrolines as metal complexing agents and their use in analytical applications has provided the impetus for an extensive study of procedures for their synthesis.182 The original synthesis of 1,10-phenanthroline by a double Skraup reaction on o-phenylenediamine using glycerol and sulfuric acid in the presence of an oxidizing agent continues to attract attention, and various improvements in reaction... 

The ability of 1,10-phenanthroline and its derivatives to form complexes with metals and nonmetals is well known. The subject has... 

Phenanthroline and its derivatives have pronounced effect on many biological systems. The activity in many cases is due to the ability of 1,10-phenanthroline to complex with metals essential to the functioning of enzymes in living organisms. Some reports, however, indicate that factors not concerned with its ability to bind metal ions are also important.375,376,382,395... 

The principal use of 1,10-phenanthroline and several of its derivatives is, of course, as analytical reagents particularly for the determination of metals and in the form of their metal complexes as oxidation-reduction indicators. These uses of 1,10-phenanthrolines have been well... 

Typical OH-scavengers suppress this reaction of (OP)2Cu+ (Que et al. 1980) yet, acetate and benzoate seem to be equally efficient, despite the fact that acetate is nearly two orders of magnitude less reactive towards OH than benzoate (k=7 X 107 dm3 mol-1 s 1 vs k = 5 X 109 dm3 mol-1 s 1 Buxton et al. 1988), and obviously it is not a freely diffusing OH that is responsible for the reaction. The reaction is also suppressed by Cu-complexing compounds and by transition metal ions such as Zn2+, Co2+, Cd2+ and Ni2+ that form stable complexes with 1,10-phenanthroline (Que et al. 1980) and also by competitive intercalators such as ethidium bromide and 2,9-dimethyl-l,10-phenanthroline (Reich et al. 1981). Interestingly, compared to its parent, the latter is inactive. NADH may serve as a reductant, but 02, seems to be a salient intermediate in this cleavage reaction, because cleavage is fully suppressed in the presence of SOD (Reich et al. 1981). 

There are several excellent photosensitizers one of them is [Ru(bpy)3]2+ [6]. There are two optical isomers in this complex one is A [Ru(bpy)3]2+ and the other is A-[Ru(bpy)3]2 +, as shown in Scheme 1. Thus one can expect to perform the stereoselective electron transfer reaction with A- and A-[Ru(bpy)3]2 +. Unfortunately, however, the racemization of [Ru(bpy)3]2+ is induced photochemically [7]. The reasonable way to suppress the photoracemiza-tion of this complex is to introduce the optically active organic functional group into the transition metal complexes, as will be discussed in Sec. II.B. The other photosensitizer that is useful for the photoinduced electron transfer reaction is the copper(I) complexes with 1,10-phenanthroline and their derivatives [8,9]. Zinc(II) porphyrin is also an excellent photosensitizer for photoinduced electron transfer reaction [10]. In these complexes, molecular chirality does not exist, unlike in [Ru(bpy)3]2 +. Thus one must introduce some chiral functional group into these compounds, to use these complexes as chiral photosensitizers. 

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