Zinc complexes ligand modification

Modification of the Schiff-base ligand by introduction of two bromine substituents in H298 resulted in the isolation of a tetrametallic species [YbZn(98)]2(/r-OH)2 (fig. 84) when the zinc complex was treated with ytterbium trichloride. Typical Yb(2F5/2) emission takes place upon ligand excitation, both in acetonitrile and in methanol, with an intensity larger than the one exhibited by the related bimetallic complex [Zn(98)(ac)Yb(N03)2] (Yang et al., 2005). 

Metal complexes with Schiff base ligands have useful applications in organic optoelectronics due to their outstanding photoluminescent (PL) and electroluminescent (EL) properties, and their ease of synthesis, which readily allows structural modification for optimization of material properties.28 Hamada and co-workers pioneered the use of zinc(II) Schiff base complexes as blue to greenish white emitters for EL devices. We have demonstrated Pt(II) Schiff base triplet emitters as yellow dopants for organic light-emitting devices... 

Two crystalline modifications of mercury(n) NN-diethyldithiocarbamate have been reported.208 The a-form consists of dimeric Hg2(S2CNEt2)4 units, in which the metal atom is five-co-ordinate, in a manner similar to analogous zinc and cadmium complexes. The P-form is composed of essentially monomeric Hg(S2CNEt2)2 units, with the two ligand molecules co-ordinated in a plane through the S atoms (Hg—S = 2.40 A). 

In order to increase the solubility of porphyrin and phthalocyanine complexes, several structural modifications have been made, a, jS, y, 6-Tetra-(4-pyridyl)-porphin complexes of copper(II), nickel(II), and zinc(II) have been synthesized (35) and their ultraviolet spectra determined in chloroform and in acid solution. By utilizing sulfonic acid groups to increase solubility, complexes of 4,4, 4",4" -tetrasulfophthalocyanine complexes of many metals were prepared (94j 95). This chelating agent was found to have a ligand field strength comparable to cyanide (94y 95). 

The metalloporphyrins as macrocyclic compounds have a few sites for specific and universal solvation and are able to axial coordination of some ligands. At the present time chemical modification of macrocycle is a main way of increasing of selectivity of molecular complex formation. The data obtained earlier [1,2] show that the selectivity may be increased due to specific %-% interactions of the metalloporphyrins with aromatic molecules. Aromatic molecules coplanar to the macrocycle will rise geometrical requirements to axial coordinating ligands. In particular, the results of the thermodynamic study of the axial coordination of n-propylamine by zinc(II) porphyrins in benzene have demonstrated the formation of the complexes of the metalloporphyrin containing both w-propylamine and benzene [2], The aim of this work is to study the molecular complexes of zinc (II) porphyrins prepared by slow crystallization from saturated solutions in benzene, w-propylamine and mixed solvent benzene - -propylamine. 

The modifications of the Gilman-Speeter reaction include the activation of zinc by tri-methylsilyl chloride (TMSCl) and the application of lithium ester enolate" or lithium thioester enolate as the substitute for the traditional Reformatsky reagent. In these modifications, it was found that TMSCl-activated zinc is much more effective in promoting the reaction between ethyl bromoacetate and Schiff bases. In addition, in the presence of a chiral ether ligand, the reaction between lithium ester enolate and imines affords 0-lactams of high enantiomeric excess, probably due to the formation of a ternary complex reagent. " The enantioselectivity and reactivity of the ternary complex depend on the size and nature of the lithium amide used. For example, the lithium amide from 2,2,6,6-tetramethylpiperidine (LTMP) is unfavorable for this reaction." ... 

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