Copper complexes nitrogen ligands

Phosphino-oxazoline)copper complex 28 was found by Helmchen et al. to be an excellent Diels-Alder catalyst [37] (Scheme 1.47, Table 1.20). The nitrogen atom acts as an electron-donating ligand, whereas phosphorus is a cr-donor-Tt-acceptor ligand. The copper complex of this phosphino-oxazoline ligand is therefore expected to have... 

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]. 

The complex trans-[Cun(hfac)2(TTF—CH=CH—py)2](BF4)2-2CH2Cl2 was obtained after 1 week of galvanostatic oxidation of Cun(hfac)2(TTF CH=CH py)2 [61]. The molecular structure of the copper complex is identical to its neutral form. There is one TTF CH=CH py molecule per BF4 and one dichloromethane solvent molecule. The copper is located at the center of a centrosymetric-distorted octahedron two TTF CH=CH py ligands in trans- conformation are bonded to Cun by the nitrogen atoms of the pyridyl rings. From the stoichiometry, the charge distribution corresponds to fully oxidized TTF CH=CH—py+" radical units. 

Calixarenes, when in their cone-conformation (54), represent versatile host systems for metalated container molecules and many examples have been reported in the literature (55-61). Reinaud and coworkers have carried out extensive work concerned with calix[6]arenes that are functionalized at the small rim by nitrogen arms (62), aiming to reproduce the hydro-phobic binding site of mononuclear zinc and copper metalloen-zymes. A recent example is the calix[6]arene ligand L1 (Fig. 3), in which a tris(2-methylpyridyl)amine unit covalently caps the calixarene small rim (63). The ligand forms copper complexes of... 

Copper-catalyzed ATRP is a multicomponent system, consisting of a monomer, an initiator with a transferable (pseudo)halogen, and a copper complex (composed of a copper (pseudo)halide and nitrogen-based complexing ligand). For a successful... 

Nitrogen ligands are the most donor functions in enzymes, the oldest homogeneous catalysts. Here they occur in imidazoles, porphyrins, binding to metals such as copper and iron, and they are involved in many oxidation reactions. Numerous mimics of these complexes are used in homogeneous... 

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