1,10-Phenanthroline synthesis

The aim of the present work was optimization of synthesis of SG -polymeric cation exchanger composite films by sol-gel technology in the presence of non-ionic surfactants and their application for detenuination of Zn (II) as phenanthrolinate (Phen) complex. 

Holmium, tris(2,2,6,6-tetramethyl-3,5-heptanedione)-photosubstitution, 1,408 Holmium complexes 1,3-diketones, 2,387 phenanthroline, 3,1069 Homoazaporphyrins synthesis, 2, 817 Homolytic cleavage catalysis... 

Although the number of applications of olefin metathesis to transition metal complexes is small compared to the number of applications in organic synthesis, this field is becoming increasingly important. Spectacular examples are the double RCM reactions of copper phenanthroline complexes as a synthetic route to catenanes [113] or a recently reported approach to steric shielding of rhenium complex terminated sp-carbon chains [114]. 

The synthesis of [3]- (figuratively shown as 7) and a [5]rotaxane (8) with one central and two terminal porphyrins in the open configuration has been reported <96AG(E)906> also a rotaxane with two Ru(terpy>2 stoppers has appeared <96CC1915>. A pseudorotaxane comprised of a macroring of 2,9-diphenyl-1,10-phenanthroline unit and a molecular string... 

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. 

There are very few examples of asymmetric synthesis using optically pure ions as chiral-inducing agents for the control of the configuration at the metal center. Chiral anions for such an apphcation have recently been reviewed by Lacour [19]. For example, the chiral enantiomerically pure Trisphat anion was successfully used for the stereoselective synthesis of tris-diimine-Fe(ll) complex, made configurationally stable because of the presence of a tetradentate bis(l,10-phenanthroline) ligand (Fig. 9) [29]. Excellent diastereoselectivity (>20 1) was demonstrated as a consequence of the preferred homochiral association of the anion and the iron(ll) complex and evidence for a thermodynamic control of the selectivity was obtained. The two diastereoisomers can be efficiently separated by ion-pair chromatography on silica gel plates with excellent yields. 

Hydrosilylation of dienes accompanied by cyclization is emerging as a potential route to the synthesis of functionalized carbocycles. However, the utility of cycliza-tion/hydrosilylation has been Umited because of the absence of an asymmetric protocol. One example of asymmetric cycUzation/hydrosilylation has been reported very recently using a chiral pyridine-oxazoUne ligand instead of 1,10-phenanthroline of the cationic palladium complex (53) [60]. As shown in Scheme 3-21, the pyridine-oxazoUne Ugand is more effective than the bisoxazoUne ligand in this asymmetric cyclization/hydrosilylation of a 1,6-diene. 

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). 

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. 

Synthesis of TTF-phenanthroline macrocycles (e.g., 13) were accomplished in a simple multi-step sequence the macrocyclization procedure was from the 2,9-di(p-hydroxyphenyl)-1,10-phenanthroline with TTF-diiodide under high dilution conditions in the presence of CS2CO3 <00CC215>. 

Synthesis and Characterization of N-[l,10-Phenanthroline]-N -[(Benzo-15-Crown-5)yl] Thionrea and Its Complex with Copper(I)... 

In this study, we report synthesis of a new thiourea derivative (2) which contain crown ether and phenanthroline ring by the reaction of 5-amino-1,10-phenanthro-line with 15-isothiocyanatobenzo[15-crown-5] (1) (Fig. 43.1) and its complex with Cu(I) is obtained. The structures of the ligand and the complex were determined by their elemental analysis, UV-vis, FTIR, H NMR (DMSO-d ), C NMR (DMSO-dg) and Mass spectra (LC-MS). 

Fig. 6.1 Synthesis of a cuprocatenane. High dilution conditions for the second step allow the in-tremolecular condensation of the terminal OH groups on a single phenanthroline. Removal of the metal from the copper(I) complex by treatment with Me4N + CN in acetonitrile/water affords the catenand. Reproduced with permission from C. O. D. Buchecker, J.-P. Sauvage and J.-M. Kern, J. Amer. Chem. Soc. 106, 3043 (1984). (1984) American Chemical Society.

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