Phenanthroline derivative

Ligand 92 was readily prepared by reaction of (+)-pinocarvone with 1-phenacylpyridinium iodide. The authors similarly prepared corresponding 5,6-dihydro-1,10-phenanthrolines derived from (+)-pinocarvone and a tetrahydroquinolone (structure 93, [127]) and obtained up to 81% in the palladium-catalyzed test reaction. Chelucci et al. [ 128] reported the synthesis of chiral Ci-symmetric 1,10-phenanthrolines incorporated in asteroid backbone. Structure 94 derived from 5o -cholestan-4-one in Scheme 51, allowed very high yield and up to 96% ee using BSA and tetrabutylammonium fluoride to generate the malonate anion. 

Optical sensors for oxygen are among the few sensors, which have found practical application for process-monitoring and clinical diagnostics. They are generally based on compounds such as platinum porphyrins or ruthenium phenanthroline derivatives (Table 17) which show a decrease in luminescence upon exposure to molecular oxygen15. 

Mixed-ligand Cu(II) complexes with salicylato and phenanthroline derivatives as ligands can also be highly cytotoxic (231). Mixed-ligand Cu(II) amino acid phenanthroline complexes (Casiopeinas) such as [Cu(L-Ser)(phen)(H20)]+ 52 are reported to be effective anticancer agents (232). It is possible that a complex in this class will soon enter clinical trials. 

In the synthesis of concave 1,10-phenanthroline cyclophanes 21 (Scheme 4), the aryl bridgeheads could be easily introduced by the addition of two aryl lithium moieties 16 to 1,10-phenanthroline (15). Although aryl lithium compounds may also be added to pyridine [23], this approach could not be realized for the construction of concave pyridine cyclophanes 29 yet [24]. Therefore another route for the synthesis of the concave pyridines 29 was used (Scheme 5) the cyclization of 1,5-diaryl substituted Cj-units 23 or 27 with ammonia. The resulting 2,6-bis(2,6-dimethoxyphenyl)pyridine 24 [25], the pyridine analogue to the tetramethoxy-1,10-phenanthroline derivative 17, was then treated in the same way. After liberation of the phenol functions, the four OH groups of 28 were reacted with two equivalents of diiodides 19 [25]. As in the synthesis of the concave 1,10-phenanthroline cyclophanes 21, two macrocycles were formed in one reaction step. 

The complexes [Rh(bipy)3]3+, [RhCl2(bipy)2]+ and [Rh(OH2)2(bipy)2]3+ also catalyze reaction (70), with the latter two being most effective. Using sulfonated bipyridyl or phenanthroline derivatives, water-soluble catalysts were prepared.444... 

The electrophilic reactions of co-ordinated 1,10-phenanthrolines are not always as simple as might be expected. Thus, the nitration of cobalt(m) 1,10-phenanthroline complexes yields 5-nitro-1,10-phenanthroline derivatives at low temperature, but prolonged reaction in hot solution leads to further reaction and oxidation of the ligand to give excellent yields of 1,10-phenanthroline-5,6-quinone complexes (Fig. 8-40). Even after the formation of the quinone, the complexes may exhibit further reaction. For example, reaction of the l,10-phenanthroline-5,6-quinone complexes with base results in the formation of a complex of 2,2 -bipyridine-3,3 -dicarboxylic acid (Fig. 8-41)... 

Figure 10.67 The 2 1 complex between 1,10-phenanthroline derivative 10.102 and Cu(I) along with cartoon schematic.75...

The lower energy luminescence of Os(II) complexes relative to the corresponding Ru(II) complexes has led to a number of studies seeking complexes that absorb throughout the visible (black chromophores) and have emissive excited states in the near-infrared. Kol and Barigelletti reported the photophysical properties of Os(II) complexes of eilatin (eil, Scheme 1) and isoeilatin (ieil) bis-phenanthroline derivatives. The eil com-... 

Fe(Y-phen>2X2] Complexes with Mono-substituted Phenanthroline Derivatives. .. 112... 

Table 5. Magnetic data of [Fe(phen-2-Y)2] nH20 and [Fe(phen-2-Y)2 X2-nHjO complexes with tridentate phenanthroline derivatives...

One process which is related to the photocyclization of stilbene-like substrates is the conversion of 2-vinyl biphenyls to 8,9a-dihydrophenanthrenes, which undergo a facile thermal isomerization to 9,10-dihydrophenanthrenes (Scheme 9.24) [36]. For the synthesis of 5,6-dihydro- 1,10-phenanthroline and 1,10-phenanthroline derivatives, metal-chelation of the nitrogen atoms has shown to be productive (Scheme 9.25) [37]. 

Dicyanobis(2,2 -bipyridine)iron(II) can be prepared in a manner analogous to that of the 1,10-phenanthroline derivative, since 2,2,-bipyridine and 1,10-phenanthroline behave similarly. 

The iron phenanthroline derivative in Scheme 9 is a source of cyclobutadiene which can be trapped by maleanil. Both reactants bound to a polymer give, when oxidized, the polymeric adduct shown. By methaminolysis a derivative is formed, proving that cyclobutadiene is a free-existing intermediate in this reaction (74). 

Oxygenation reactions of Pd(0) have been revisited recently in order to gain fundamental insights into this catalytically important reaction, and these studies have employed both phenanthroline and NHC ligands [43-45]. The use of bathocuproine (be), a phenanthroline derivative, enabled isolation and crystallographic characterization of (bc)Pd(r 2-02) [43] (Scheme 2). Addition... 

The direct electrochemical oxidation of NAD(P)H is possible but for this purpose relatively high oxidation potentials are necessary and potential passivation of the electrodes can occur. Because of the low speed of NADH oxidation and to avoid fouling of the electrodes, mediators like phenanthroline derivates are often used for advanced electron transfer. Those systems can be coupled efficiently with enzyme-catalyzed reactions which require NAD(P)H oxidation. 

The two phases incorporating the tetranuclear molybdate core, 14 and 15, are the only isomorphous pair to be revealed to date. This may suggest that under appropriate conditions, isomorphous phenanthroline derivatives of 4, 9,12 and 16 may be accessible. 

Chen [1] prepared imidazole-fused phenanthroline derivatives, (I), that were effective as organic light-emitting devices. 

Zhuang Q, Zhou D, Tu S et al (2008) A highly efficient microwave-assisted synthesis of chromeno[3, 4-b][4, 7]phenanthroline derivatives through multi-component reactions in water. J Heterocycl Chem 45 831-835... 

Bian, Z.Q., Wang, K.Z., and Jin, L.R (2002) Syntheses, spectroscopic and crystal structural studies of novel imidazo [4,5-f]l,10-phenanthroline derivatives and their Eu(lll) ternary complexes with dibenzoylmethane. 

Bian, Z.Q., Gao, D.Q., Guan, M., et al. (2004) Electroluminescent properties of three ternary europium complexes with different phenanthroline derivatives. Science in China (Series B), 47, 326-334. 

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