3,4,7,8-Tetramethyl-1,10-phenanthroline, ligand

Allyl vinyl ethers may be prepared via stereospecific copper-catalyzed coupling of allyl alcohols and vinyl halides. For example, the copper catalyst derived from the tetramethyl 1,10-phenanthroline ligand shown below facilitates C-0 bond formation between ( )-vinyl iodides and allyl alcohols when the reaction mixture is heated in the presence of air. ... 

Metal chelates contain 1 1 molar ratio of ligand to metal ion. TMEN = tetramethyl-ethylenediamine DMEN = dimethylethylenediamine DIPY = a,a -bipyridine PHEN = o-phenanthroline HEN = iV-hydroxyethylethylenediamine DHEN = JV ,iV /-dihy-droxyethylethylenediamine. 

Substituted bipyridines and phenanthrolines have been used as ligands for copper(II) ions. 4,4 6,6 -Tetramethyl-2,2 -bipyridyl(L) gives monomeric CuL(N03)2, two sulfato complexes, and a series [CuL2X]+C104, as well as forming copper(I) complexes readily (309). 2,9-Dimethyl-1,10-phenanthroline affords 1 1 complexes with cupric... 

It is well known that alkali and alkaline earth cations are very difficult to complex due to the configuration of the rare gas electronic structure of these ions. Fortunately, some specific ligands are known, such as aprotic dipolar solvents (dimethylformamide, sulfolane, dimethylsulfoxide, N-methyl pyrolidone and so on), aminoxides, phosphinoxides, glymes and polyethylene glycols, crown ethers and cryptates, bidentate amines (tetramethyl ethylene diamine, 1,10 phenanthroline, etc. [14, 53, 61, 68]. 

Ferroin , Fe(phen)3, has been used since 1933 as a redox indicator because with the first excess of oxidant Fe(phen)3 is immediately formed with a concomitant colour change from red to blue this redox reaction is reversible. By introducing substituents the redox potential is altered to give a range of indicators from which the correct one can be chosen for each situation, Values of (volts) in 1 M H2SO4 are as follows 5-nitro (1.25), 5-sulfono (1.20), ferroin itself (1.06), 5-methyl (1.02), 5,6-dimethyl (0.97), 4,7-dimethyl (0.88), and 3,4,7,8-tetramethyl (0.81). 2,3,4-Substituted phenanthroline complexes of Fe and Cu show a linear relationship between q and the dissociation constant of the ligand. 

The synthetic methods of Equation 5 also proved good for the use of phenanthroline and substituted phenanthrolines as ligands. We were able to prepare and isolate complexes with 1,10-phenanthroline, 3,4,7,8-tetramethyl-l,10-phenanthroline, and 4,7-diphenyl-l,10-phenanthroline substituting for bipyridine. 

A further improvement was achieved by employing 3,4,7,8-tetramethyl-1,10-phenanthroline (33) as ligand. The combination of NiCla and 33 catalyses cross-coupling of aliphatic iV-tosylaziridines and primary alkylzinc reagents under mild conditions. In this transformation the carbon-nitrogen bond cleavage mainly occurs at the less-hindered side of the aziridine (Scheme 14.40). In addition, when enantiopure benzylaziridine was... 

The administration of robust complexes such as those of Pt or Au will be of use when their reactivity with the target is pharmacokinetically appropriate — the window of reactivity must be recognised and will depend on chemical factors such as hydrolysis and ligand exchange as well as uptake and distribution. Uptake of metal complexes may be best for neutral species, since no transport process need be activated but it is well to remember that this is not an absolute requirement. The charged amine complexes, close analogues of cisplatin, enter cells (Chapter 3.1) and indeed lipophilicity may enhance this uptake an example is the ruthenium (II) chelate of (3,4,7,8-)tetramethyl-l,10-phenanthroline (Chapter 6.1.3). 

The ubiquitous chelates of 1,10-phenanthroline were studied some time ago for their antiviral activity [17]. The inhibitory effect of various chelates on the multiplication of influenza virus (Melbourne strain) in chick chorioallantoic membrane in vitro was studied, and the most effective complex was shown to be the [Ru(acac) (3,5,6,8-Me4-l,10-phen)2] cation, which inhibited multiplication at concentrations of 6 X 10 M(—log M = 6.2). Other chelate complexes were active at concentrations of 10 to 10 M. A structure—activity study of metal chelates showed, however, that for a given chelate ligand, more labile complexes such as those of Cd or Cu were more active than their inert counterparts, the order for doubly-charged (2+) chelates being Cd(II) > Cu(II) > Zn(II) > Mn(II) > Fe(II) > Co(II) > Ni(II) > Ru(II) [18]. This correlation coincided with that found for some antibacterial effects (Chapter 9). Further studies showed that the virostatic activity may be manifested by either direct inactivation of the virus (possibly through dissociation of the more labile chelates) or by direct action on the host cell (for inert complexes). The latter effect is indicated by the fact that the trend in virostatic activity is similar to that in antitumour activity [19] (see also Chapter 6) and the fact that, of the various 1,10-phenanthrolines studied, the tetramethyl derivatives most easily penetrate cells [20]. 

C-0 Bond Formation. A simple and mild method for the coupling of aryl iodides and aliphatic alcohols catalyzed by copper iodide which does not require the use of aUcoxide bases has been described. The reaction can be performed in neat alcohol or in toluene as solvent with catalytic quantities of Cul and 1,10-phenanthrohne, and 2 equiv of CS2CO3. This methodology was successfully applied to the formation of allyl vinyl ethers with tetramethyl-l,10-phenanthroline as the ligand. iVAl-Dimethyl glycine is also a good ligand for this copper iodide-catalyzed Ullmann-type diaryl ether synthesis between phenols... 

In a typical example, the reaction of Af-methylbenzylamine with diethylsilane was carried out in the presence of [Ir(cod)(OMe)]2 afforded hydridosilylamine. Subsequently, the reaction of the resulting hydridosilylamine in the presence of [Ir(cod)(OMe)]2 combined with 3,4,7,8-tetramethyl-l,10-phenanthroline as a ligand and norbornene as hydrogen acceptor at 80 "C led to the corresponding aza-silolane derivatives in 95% yield (Scheme 11.7, Figure 11.2). 

---