Investigation On Carbon-Carbon Bond Cleavage Of Acetonitrile Catalyzed By Copper Complexes&Syntheses And Properties Of Coordination Complexes With1,10-Phenanthroline Derivate Ligands

Acetonitrile is widely used as an organic solvent because of its stability and polarity. Due to the lone pair electrons on the terminal nitrogen atom, acetonitrile also has been employed as a ligand in metal complexes, from which it can be replaced by other ligands. However, the C-C bond cleavage of acetonitrile catalyzed by metal centers has been seldom reported. The achievement of cleaving the C-C bond of acetonitrile by common pyridyl copper complexes in homogeneous media and mild conditions remains a challenge.Aromatic heterocyclic derivate compounds of1,10-phenanthroline bearing delocalized π-systems are often formed by donor-acceptor (D-A) spacers. The bidentate chelate nitrogen atoms in1,10-phenanthroline are easily coordinated with metal ions. These ligands have potential applications on organic and polymeric light-emitting devices, field-effect transistors, photoconductive materials and photovoltaic solar cells. Advanced functional materials might be achieved by combination of rare earth ions and1,10-phenanthroline derivate ligands which are functionalized by optical-sensitive thiophen groups.The content includes two parts as follow: 1. The C-C bond cleavage of acetonitrile catalyzed by pyridyl copper complexes in homogeneous media and mild conditions has been investigated in the presence of certain organic reductants.This novel reaction has been systemically investigated by altering anions of copper complexes, organic reductants, pyridyl ligands, reagent molar ratios, solvents and reaction time. Some results have been obtained. For instance, different counterions of copper complexes exhibit a reactivity order of ClO4->BF4-> PF6-> NO3-≈SO42-Cl-≈0. Two kinds of organic reductants (aryl aldehydes and pyridyl amines) have been employed in this reaction. Aryl aldehydes exhibit weaker reductive ability than pyridyl amines, but more complicated complexes are produced by using pyridyl amines. With the study of extensive pyridyl ligands, it is suggested that copper complexes bearing pyridyl ligands free of oxidative groups can be used to catalyze the C-C bond cleavage of acetonitrile in reductive atmosphere.During the investigation of this novel reaction system, many copper complexes have been obtained, including mono-, di-, tri-and tetranuclear copper complexes as well as one-dimensional coordination polymers1-17with the ligand CN-, and also some copper complexes18-25without CN-. Cobalt(Ⅲ) complex26bearing ligands CN-has been obtained with a high yield by the in situ reaction between a cobalt(Ⅲ) salt and a resulting solution of the anterior catalytic reaction. Thus, it is suggested that low toxic acetonitrile might be used as a potential novel cyanic resource to replace severely toxic cyanides. In addition, some mixed-valent copper complexes obtained from this novel reaction have been employed as catalyzers in the oxidation of benzaldehyde as well as the C-N bond coupling Ullmann reactions. Considerable catalytic efficiencies have been achieved in these reactions.2. Two species of thiophen functionalized1,10-phenanthroline ligands have been used to prepare transition matel and rare earth complexes27-55. The luminescent properties have been investigated and discussed.Hg(Ⅱ), Ni(Ⅱ), Ru(Ⅱ) and La(Ⅲ) complexes with the ligands TIP and5-Br-TIP, the5,6-derivate1,10-phenanthroline ligands, have been synthesized. Their luminescent properties and structural characters have been emphasized because of the delocalized π-system as well as the planarity of the ligands. Specially, not only the ligands, but also the whole molecules/cations of dinuclear metal complexes32and33exhibit excellent planarity, forming the2.52nm and2.90nm linear complexes, respectively.TP, MTP and BMTP, the3,8-derivate1,10-phenanthroline ligands, have been employed in the synthesis of rare earth coordination complexes with another β-diketone ligand. The luminescent properties of Eu(Ⅲ) complexes with different β-diketone ligands TTA and DBM as well as different1,10-phenanthroline derivate ligands TP, MTP and BMTP have been investigated at room temperature and low temperature conditions. The results have shown that Eu(Ⅲ) complexes with β-diketone ligand TTA always exhibit much larger luminescent intensities than Eu(Ⅲ) complexes with β-diketone ligand DBM, although the latter ones have greater increased coefficients at low temperature than frontal ones. Moreover, Eu(Ⅲ) complexes with ligand MTP exhibit much larger luminescent intensities than Eu(Ⅲ) complexes with ligand TP, while Eu(Ⅲ) complexes with ligand TP exhibit a little larger luminescent intensities than Eu(Ⅲ) complexes with ligand BMTP.