4 -Phenyl-2,2 :6’,2"-terpyridine

Phenylmethylsilanediol, synthesis, 42 155 Phenylsilanetriol, monosodium salts, 42 169 4 -Phenyl-2,2 6, 2 -terpyridine bis nickel complex, 30 74 molecular structure, 30 74 PhjtfluorenyllSiOH, 42 197 (Ph(Me2N)C-=Nli], 37 59-65 orientation of imino ligand, 37 61-63 (PhMe SiljCSiH OH, 42 244-245, 248 (PhMe SiljCsiMeHlOH), 42 191 Phosphaalkenes acyclic, 33 338-353 butadienes, 33 346-349 cumulenes, 33 352... 

In the case of terpyridine and acridine derivatives, the bis(methylamines) are the most convenient intermediates. Substituted 4/-phenyl-2,2/ 6/,2"-terpyridines were prepared by reacting (ii)-propenons and iV-[2-(pyrid-2 -yl)-2-o octln l p ridinium iodide with ammonium acetate in acetic acid or in methanol. The terminal pyridine moieties were oxidized with 3-chloroperbenzoic acid to iV, A" -dio idcs followed by modified Reisserty-Henze reaction to obtain 6,6"-dicarbonitriles. The bis(methylamines) were obtained by reduction of the 6,6"-dicarbonitriles withborane (scheme 8 (Mukkala et al., 1993)). 

Nomenclature is always a vexing subject the ligand (Fig. 1) has been known variously as 2,2, 2"-tripyridyl, 2,2, 2"-tripyridine, 2,6 -bis(2-pyridyl)-pyridine, and 2,2 6, 2"-terpyridine. The latter is the systematic name (262) and will be used throughout this article. All other compounds will be named systematically, according to lUPAC recommendation A-54. In this article, the abbreviations terpy, quaterpy, quinquepy, bipy, and phen will be used for the ligands in Figs. 1-5, respectively. Substituted derivatives will not be similarly described thus 4,4"-diethyl-4 -phenyl-2,2 6, 2"-terpyridine (Fig. 6) will be denoted 4,4"-Et2-4 -Phterpy. 

Fig. 8. The crystal and molecular structure of 4 -phenyl-2,2 6, 2"-terpyridine (a) and its bis complex with nickel(II) (b) 129).

Phenyl-2,2 6, 2"-terpyridine reacts with [ Cp M(ju-Cl)Cl)2] (M = Rh, Ir) in methanol with sodium tetrafluoroborate to yield mononuclear cationic 9 (M = Rh, Ir) with the bidentate coordination mode and fluxional behavior of the ligand (98POL299). 1,4-Bis(2,2 6, 2"-terpyridyn-4 -yl)benzene with the same rhodium(III) and iridium(III) precursors forms dinuclear 10 (M = Rh, Ir) where the polypyridine ligand is still bidentately coordinated and fluxional. 

Constable, E.C., Henney, R.P.G., Leese, T.A. and Tocher, D.A. (1990) Cyclometallation reactions of 6-phenyl-2,2 -bipyridine a potential C,N,N-donor analogue of 2,2 6, 2"-terpyridine. Crystal and molecular structure of dichlorobis (6-phenyl-2,2 -bipyridine)ruthenium(II). Journal of the Chemical Society, Dalton Transactions, (2), 443. 

The spin state of iron(II) in substituted 2,2 6, 2"-terpyridine, (72), complexes depends on the position of bulky substituents—phenyl substituents in both the 6 and 6" positions give a high-spin complex phenyl substituents in the 4 and 6 positions give a complex which exists both in high-spin and in low-spin forms. Crystal structure determinations gave Fe—N bond distances in both forms of the 4,6-diphenyl complex and of the 6,6"-diphenyl complex. Each ligand in the latter com )lex has one terminal pyridine very weakly bonded to the iron, with... 

Spectroscopic data of la—li, monomers of la—li, and model compound 1 (zinc(II) fe(V-phenyl salicylaldiminato) are listed in Table 2. The absorption spectra of these zinc(II) terpyridine polymers are similar, with absorption maxima at 286—290 and 320—391 nm. PL of these polymers span violet, blue, green, and yellow color. The PL quantum yields ( I>PL) range from 25% for lb and le to 77% for If in DM Ac. The PL values of the polymer thin films were determined using integrating sphere,23 which were found to vary from 0.15 to 0.55 0.05 (Table 2). 

Barigelletti F et al (1993) Luminescence properties of rigid rod-like binuclear ruthenium(II)-osmium(II) terpyridine complexes - electronic interaction through phenyl bridges. JCS Chem Commun 942-944... 

The easiest reactions are those in which the nucleophile is the gold-activated species. Examples of this are Au(I)-catalyzed carbene and nitrene transfers (equations 142 and 143) that convert olefins into cyclopropanes or aziridines, respectively. In the carbene transfer, ethyl diazoacetate is the source of carbene and the active NHC-gold cationic catalyst is generated by chloride abstraction with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate NaBAT4. The cyclopropanation is competitive with other carbene insertions with active C H or N H bonds present in the substrate. For the aziridinations of olefins, nitrene formation is accomplished by the oxidation of sulfonamides with PhI(OAc)2 and the catalyst of choice is a gold-(I) triflate with a terpyridine ligand. 

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