Ruthenium 1.2- bis

Beer, P. D., Szemes, F., Remarkable chloride over dihydrogen phosphate anion selectivity exhibited by novel macrocyclic bis [ruthenium(II) bipyridyl] and ruthenium(II) bipyridyl-metallocene receptors. J. Chem. Soc., Chem. Commun. 1995, 2245-2247. 

Bis(ruthenium dichloride-S-BINAP)-triethylamine catalyst Ruthenium, bis[[1,1l-binaphthalene]-2,2 -diylbis[diphenylphosphine]-P,P ]di-p-chlorodichloro(N,N-diethylethanamine)di- (114717-51-0), 77, 3... 

Figure 14. Kb values, from intervalence measurements, on a log scale, as a function of the through-space metal-metal distance +, ruthenium bipyridylpolyene complexes (series 1) , ruthenium bis(terpyridyl) complexes (series 2) , ruthenium bis(cyclometallated) complexes, dipyridylbenzene family (series 3) , ruthenium bis(cyclometallated) complexes, phenylpyridine family (series 4) A, bis(ferrocenyl)polyenes (series 5). Additional measurements a, bis(cyclometallated) complexes, phenylpyridine family with diethynylanthracene as spacer b, bis(ferrocene) with three phenylene and four vinylene units as spacer c, bis[ruthenium(trisbipyridyl)] with five double bonds as spacer. Note that the Cp (dppe)Fe system bridged by octatetrayne (13 A, 0.32 eV) is outside the graph.

Platinum and palladium complexes of thietane and 3,3-dimethylthietane have been prepared as illustrated for 90. The platinum complexes exist in cis and trans configurations, but no cis-trans isomerization of the palladium complexes in the solid state was observed. Stability constants of thietane with Mn(ll), Co(II), and Ni(II) chelates have been determined. Proton nmr studies show that the absorption of the a-methylene protons, which are syn to the metal, is shifted downfield (about 0.7 ppm) more than the absorption of the protons anti to the metal (about 0.4 ppm downfield). Energies of activation for pyramidal inversion were determined. Bis-ruthenium complexes of di-, tri- and tetraspirothietanes (e.g., 90a) show rapid electron transfer between the ruthenium ions long-range electron tunneling was proposed. ... 

It is noteworthy that few of the receptors discussed so far exhibit specific binding and sensing of the chloride anion, yet this substrate is crucial for a large number of biological processes (261). The novel macrocyclic bis[ruthenium(II)bipyridyl] and ruthenium(II) bipyridyl-metallocene receptors (140-142) have been prepared. The H NMR titrations indicated that each re-... 

Structural changes, accompanied with the reduction of ruthenium complexes, were extensively investigated in the case of the 2-electron reduction product of 195 (196 in Fig. 49) [174]. The X-ray structure analysis of 196 shows an unusually small distance between the quarternary carbons C-3 and C-14 the measured value of 196 pm seems to be the longest carbon single bond determined by X-ray structure analysis till now [174], The conformation of the two benzene rings is best described as similar to those found in cyclohexadienyl anions. Comparison with the spectroscopic data of other bivalent positive bis(ruthenium) complexes led to the assumption that the cyclohexadienyl anionic re-decks are present as well [174]. 

Comparisons of the redox properties with those of bis(ruthenium) complexes of polycyclic arenes like phenanthrene [178,179] show that the electron transfer here can be even faster [179]. 

The bis-ruthenium species 45 (Chart 5.12) has been prepared and characterized via an X-ray crystal structure [54]. No splitting is observed in the reduction waves, suggesting that the interaction between metal centers is weak, but the thiophene oxidation is shifted positive due to the electron-withdrawing nature of the metal groups. 

Quite recently we also succeeded in X-ray structure determination of the mono-metallated complex of 1 with (Cp Ru)+ [64]. As in the bis-ruthenium analog the metal was 7 coordinated to one of the benzene rings of 1 on its exo (convex) face. This is the first experimental evidence demonstrating the exo preference of 7 coordination of (Cp Ru)+ to corannulene. Also, another bis-metallated complex, [(Cp Ru)2( 2 / / C2oHio)][SbF6]2 was prepared and characterized by X-ray [64]. 

Dynamic equilibrium between the bis-ruthenium metallomacrocycle 325, ligand syn-tone 241, and a RueLg coordination capsule 629 (Scheme 4.96) is reported in [93] to be shifted in the direction of the corresponding host-guest 1 2 cage complex by addition of coronene as an appropriate guest In this coordination capsule, the triazine ligand syntones are stacked on top of each other, and two coronene molecules are sandwiched between them. 

Vectorial transfer of electronic energy in rod-like ruthenium-osmium complexes with bis-2,2, 2"-terpyridine ligands 97CC333. 

Imidazole is characterized mainly by the T) (N) coordination mode, where N is the nitrogen atom of the pyridine type. The rare coordination modes are T) - (jt-) realized in the ruthenium complexes, I-ti (C,N)- in organoruthenium and organoosmium chemistry. Imidazolium salts and stable 1,3-disubsti-tuted imidazol-2-ylidenes give a vast group of mono-, bis-, and tris-carbene complexes characterized by stability and prominent catalytic activity. Benzimidazole follows the same trends. Biimidazoles and bibenzimidazoles are ligands as the neutral molecules, mono- and dianions. A variety of the coordination situations is, therefore, broad, but there are practically no deviations from the expected classical trends for the mono-, di-, and polynuclear A -complexes. 

In accordance with FMO theory predictions,273 C2 —C4is the preferred modeofcycloaddition of tricarbonyliron and -ruthenium complexes of methyl l//-azepine-l-carboxylate with ethenetetracarbonitrile,222,274 hexafluoroacetone,222 and 2,2-bis(trifluoromethyl)ethene-l,l-dicarbonitrile 222 however, with ethenetetracarbonitrile, tricarbonyl[f/4-l-(ethoxycarbonyl)-1/f-azepine]iron(0) (1) yields a 1 6 mixture of the predicted C2 —C4 exo-adduct 2 and the C2 — C7 [6 + 2] 7i-cycloadduct 3,222 the latter heing formed by rearrangement of the former.274 Mixtures of the two adducts are also obtained with the tricarbonyliron complexes of 3-acetyl-l//-azepine and its l-(ethoxycarbonyl) derivative.274... 

Meisel etal. [18-20] were the first to investigate how the addition of a polyelectrolyte affects photoinduced ET reactions. They found that charge separation was enhanced as a result of the retardation of the back ET when poly(vinyl sulfate) was added to an aqueous reaction system consisting of tris(2,2 -bipyridine)ruthenium(II) chloride (cationic photoactive chromophore) and neutral electron acceptors [21]. More recently, Sassoon and Rabani [22] observed that the addition of polybrene (a polycation) had a significant effect on separating the photoinduced ET products in an aqueous solution containing cir-dicyano-bis(2,2 -bipyridine)ruthenium(II) (photoactive donor) and potassium hexacyano-ferrate(III) (acceptor). These findings are ascribable to the electrostatic potential of the added polyelectrolytes. 

Figure 1.29 Synthesis of ruthenium complexes of the chelating ligand bis(dimethylphosphino)-...

Some bis(dinitrogen) complexes exist, generally as m-isomers (presumably this minimizes competition for the metal t2g electron density in 7r-bonding). Unlike ruthenium, osmium(III) dinitrogen complexes do exist, showing osmium(III) to be a better 7r-donor not surprisingly, they are more labile than the osmium(II) species. 

Fig. 2. ORTEP view of the cation in bis(trimethylphosphine)(diphenylsilanediyl)(pentame-thylcyclopentadienyl)ruthenium tetraphenylborate x acetonitrile 12 [37]...

Ruthenium, hydroxyoxobis[bis(2,2 -bipyridyl)]-chloride oxidation, 1,488 Ruthenium, iodotris(dimethyldithiocarbamato)-stereochemistry, 1, 82 Ruthenium, nitrosyl-complcxcs... 

Second-generation ruthenium-carbene complex, (tricyclohexylphosphine-[l,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene]ruthenium (IV) dichloride),4e was purchased from Strem Chemicals. 

Tricyclohexylphosphine[l,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene]ruthenium... 

In Aceton/Tetrabutylammoniumperchlorat wird Bis-[dithiocarbamato]-ruthenium(III) an Platin (-0,5 V) zum Bis- dithiocarbamato]-ruthenium(II) reduziert4. Tris-[2,2 -bi-py-ridyl]-ruthenium(II) kann bei -1,42 Volt sclektiv zum entsprechenden Ruthenium(I)-, bei —1,65 zum Ruthenium(0)-Komplex reduziert werden5. 

An unprecedented carbene insertion reaction was observed on reaction of the cationic re-arene ruthenium amidinates with trimethylsilyldiazo-methane (Scheme 145, TFPB = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate). 

Complexation via amidinate units was found in ruthenium complexes containing tri- and pentacyclic trifluoromethylaryl-substituted quinoxalines. The complex fragment [(tbbpy)2Ru] (tbbpy = bis(4,4 -di-ferf-butyl-2,2 -bipyridine) has been employed in these compounds which have all been structurally characterized by X-ray diffraction. ... 

Benzoselenadiazole (bsd) has been used as a ligand in the ruthenium complex [RuClH-(CO)(bsd)(PPh3)2]. This complex was used to catalyse the transalkynylation and catalytic demercuration of bis(alkynyl)mercurials <96CC1059>. 

A versatile route to 3-benzoheteropines has been reported starting from o-phthalaldehyde, including the first preparations of 3-benzarsepines and the parent 3-benzothiepin and 3-benzoselenepins <96CC2183>. l,7-Dihydro-l//-dibenzo[c,c]tellurepin has been prepared from 2,2 -bis(bromomethyl)biphenyl and potassium tellurocyanate and its complexes with palladium and ruthenium species have been studied, a number of mono- and binuclear complexes are formed <96RTC427>. 

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