Copper complexes amidines

Copper complexes, 5,533-750 acetylacetone hydrolysis, 2,379 photoreduction, 2.384 amidines... 

Structurally related complexes are also active initiators for the living polymerization of carbo-diimides (which are isoelectronic to isocyanates).1003 The proposed intermediate for this polymerization process is a metal amidinate (Scheme 29), and the model complex (349) has been reported to be a highly efficient catalyst, polymerizing 500 equivalents of di- -hexylcarbodiimide in less than 10 s. A more hydrolytically robust series of initiators has also been developed, based upon copper(I) and copper(II) amidinates.1004... 

Other amidinate anions normally form dinuclear copper(I) complexes with bridging amidinate ligands, although tetracopper(l) complexes have also been reported Silver(1) forms dimeric complexes with functionalized N,N -... 

Amidinate complexes of copper(I) and copper(II) have been found to catalyze the polymerization of carbodiimides. The copper catalysts are highly active even under air and oxygen. It was shown that the catalytic activity of an air-stable copper(II) amidinato complex is almost equal to that of reported air-sensitive titanium(IV) amidinate initiators. Scheme 225 illustrates the proposed reaction mechanism. ... 

Theoretical studies by Pyykkb in 1998 for [M2(NHCHNH)2] systems, M=Cu, Ag, and Au, predicted the M-M distances at the MP2 level [8]. Experimentally, systems containing amidinate ligands were known with Cu and Ag but unknown with Au. The results for the models containing silver and copper are close to the X-ray structures of [M2(ArNC(H)NAr)2], Ar=C6H4-4-Me and M=Ag, Cu. The Ag-Ag distance is 2.705 and 2.712 A and the Cu-Cu distance is 2.497 and 2.528 A at the experimental and theoretical level. Table 1.1. The hypothetical dinuclear gold(I) amidinate compound was calculated to have an Au-Au distance at the MP2 level of 2.728 A [8]. The dinuclear gold(I) amidinate complex now known proves the predicted Au-Au distance to be rather good. 

Pinacolone, o-(diphenylphosphino)benzoyl-coordination chemistry, 401 Piperidine, IV-hydroxy-metal complexes, 797 pA a values azole ligands, 77 Plant roots amino acids, 962 carboxylic acids, 962 Plastocyanin copper binding site, 557 copper(II) complexes, 772 copper(II) site in, 770 Platinum, dichlorobis(benzonitrile)-IR spectrum, 264 Platinum, cis-dichlorodianunine-antitumor activity, 34, 979 Platinum, ethylenebis(triphenylphosphine)-reactions with 5,6-dimethyl-2,l,3-benzothiadiazole, 194 Platinum blue formation, 265 Platinum complexes acetylacetone reactions, 380 amides, 491 amidines... 

Dinudear copper amidinate complexes catalyze the homopolymerization of carbodiimides. ... 

The titanium complexes are sensitive to high temperatures and the presence of oxygen or water. A more robust catalyst system is based on Cu(I) and Cu(II) amidinate complexes. Also, dinuclear copper amidinate complexes are used in the polymerization of carbodiimides. 

Copper ethylene chemistry is well developed, but reports of polymerizations based upon copper are rare. The amidinate ligand, A/,A/ -ditrimethylsilyl-benzamidinato, has been reported to support copper-catalyzed ethylene polymerizations. It is prepared from hexamethyldisilazane, benzonitrile, and tri-methylsilyl chloride. The resulting copper chloride complex, 2, when activated with methyl-aluminoxane, produced polyethylene with Mv = 820 000 and = 138 In another patent. 

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