Nitrogen-containing ligands pyridines

The reactions are usually carried out [201,202] in nonaqueous solvents (Solv) (alcohols, acetonitrile, DMF, and DMSO) which take part mainly as ligands in formed molecular complexes. Additionally to them, the nitrogen-containing bases (pyridine, bipy, 1,10-phen) were used. Co, Ni, Cu, Zn, Cd, Pb have mainly been applied as a source of complex-former. The ammonium salts are represented by halides and pseudohalides, in particular rhodanides, which have been used especially widely [664-675],... 

The oxidation of p-xylene to terephthalic acid occurs by the same general mechanism as described above for alkylaromatics. Bromide ions and nitrogen-containing ligands provide synergetic mixtures with metal salts [56-58,61]. Pyridine is one of the most efficient additives [59,60j. Oxo-centered cobalt(III) clusters have been isolated from the reaction mixtures, which can be regarded as active intermediates [34,62,63]. The optimum catalytic activity was found to be associated with the composition corresponding to Co Br py = 1 2 (1-2) [64]. 

Pyridine-based N-containing ligands have been tested in order to extend the scope of the copper-catalyzed cyclopropanation reaction of olefins. Chelucci et al. [33] have carefully examined and reviewed [34] the efficiency of a number of chiral pyridine derivatives as bidentate Hgands (mainly 2,2 -bipyridines, 2,2 6, 2 -terpyridines, phenanthrolines and aminopyridine) in the copper-catalyzed cyclopropanation of styrene by ethyl diazoacetate. The corresponding copper complexes proved to be only moderately active and enantios-elective (ee up to 32% for a C2-symmetric bipyridine). The same authors prepared other chiral ligands with nitrogen donors such as 2,2 -bipyridines 21, 5,6-dihydro-1,10-phenanthrolines 22, and 1,10-phenanthrolines 23 (see Scheme 14) [35]. 

Several pyridine containing ligands of this type have been reported by Toftlund [2]. A combination of two aliphatic and four imine nitrogen functions seems to provide a ligand field at the crossover point. A versatile class of ligands of this type is based on aliphatic diamines substituted with four alkylpyridine groups. The simplest compound of this type is tetrakis(2-pyri-dylmethyl)-l,2-ethanediamine (tpen) (18). 

Additional types of k C-k E chelating ylide complexes merit mentioning here, in addition to the species already presented, and some of them are shown in Scheme 24. The first is formed by ylides containing a pyridine functionality as substituent of the ylidic carbon. This type of ligand has allowed the S3mthesis of many loose clusters (82) of Cu, Ag, and Au which show weak metal( / °)-metal( / °) interactions. These facts have prompted the definition of a new phenomenon numismophilicity) to account for these weak interactions, uniquely shared by the three coinage metals [164]. Nitrogen and sulfur keto-stabilized ylides have been reacted with Pt and... 

Efficient epoxidation of a variety of linear and cyclic alkenes by RuClj/aq. Na(IO )/(bpy)/CH2CyO-5°C/15 h was observed [735] 5-methyl- or 3,4,7,8-tetram-ethyl-phenanthroline can replace (bpy) [736], The active species when (bpy) is present is probably franx-Ru(0)2(bpy) 103(011)3 [567, 568], Competition between epoxidation and cleavage of fran -stilbene with bidentate ligands (pyridine, oxazo-line, oxazolidine and thiophene), containing two different nitrogen heterocycles either linked or separated by a spacer together with RuCyaq. Na(IO )/CH3Cy2°C was reported [737],... 

In 1995 Schwarz et al.159 described novel heterocyclic structures able to adsorb selectively immunoglobulins. The structures contained sulfur and nitrogen. Reported ligands were 2-mercapto-pyridine,2-mercapto-pyrimidine, and mercapto-thiazoline. These structures were chemically immobilized on silica and agarose beads using epoxy-activated matrices. Binding capacities for silica based material were about 25 mg of IgG per milliliter of resin, while for agarose beads it was about 18 mg/mL. 

Bis-oxo-Ru(VI) complexes containing nonlabile oxidation-resistant nitrogen-donor ligands such as pyridine, bipyridine. 

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