Preparations And Properties Of Opper(Ⅰ) Complexes With N,P Ligands

Increased interests have been devoted to the design and synthesis of copper（Ⅰ） complexes because theraw materials are cheap, easily available and environmentally friendly compared to expensive preciousmetals. With the diverse of organic ligands used, copper（Ⅰ） complexes have been playing an increasinglyimportant role in many ways. For example, some well-defined copper（Ⅰ） complexes have been isolated asreaction intermediates to study the reaction mechanisms of copper（Ⅰ） catalyzed organic reactions; copper（Ⅰ）salts and their complexes are widely used catalysts for various organic reactions; and some highlyluminescent copper（Ⅰ） complexes are widely used light-emitting materials. A series of copper（Ⅰ） complexeswith N, P ligands were synthesized by choosing suitable organic ligands in this thesis. And the complexeswere appied to study the mechanism of copper（Ⅰ） catalyzed Goldberg reaction and and prepare luminescentmaterials.Goldberg reaction is C-N coupling reaction of amides with aryl halide. Study of reaction mechanismis help to improve the experimental conditions and broaden the substrate scope of Goldberg reaction. Inthis thesis, redox active bis（diphenylphosphino）-ferrocene （dppf） was applied as ligand to synthesizecopper（Ⅰ）-amide complexes （the key intermediate of Goldberg reaction）. Under anhydrous and anoxybioticconditions, a series of copper（Ⅰ） amide complexes （₂,6,7,8） were prepared when reaction precursor[（dppf）Cu]₂（μ-Cl）₂] reacted with acyclic amides at room temperature in dichloromethane for48h withsodium methoxide or sodium hydride as base. The structures of reaction intermediates （₂,6,7,8） werecharacterized by IR,1H NMR and X-ray crystallography （₂,6,7） methods. Reaction of reactionintermediates （₂,6,7,8） with aryl halides generated the N-arylation products of amides, accompanied bythe formation of a copper（Ⅰ） complex Cu（dppf）X （X=I or Br）, which has been determined by LC-MSanalysis. And the mechanism of Goldberg reaction were verified by the the direct coupling reaction ofcopper（Ⅰ） amide complexes with aryl halides.The effects of substitution groups of amide ligands on the mechanism of Goldberg reaction were alsostudied. The influence of steric and electronic effects of amide ligands were concluded through theisolation and determination of reaction intermediates, catalyst and products of Goldberg reaction. Theresults were help to determine further the mechanism of Goldberg reaction.Some competing reactions were found during the preparation of Goldberg reaction intermediates.when chloride-bridged copper（Ⅰ） complex [（dppf）Cu]₂（μ-Cl）₂] reacted with acetanilide in un-driedsolvent, an acetate-bridged copper（Ⅰ） complex9was obtained under N₂atmosphere where the acetateion came from the hydrolysis reaction （competing reaction） of acetanilide due to residual water insolvent. A μ-η²:η²-carbonato bridged copper（Ⅰ） dinuclear complex14was synthesized whenchloride-bridged copper（Ⅰ） complex [（dppf）Cu]₂（μ-Cl）₂] reacted with N-phenyl benzamide undercarbon dioxide atmosphere. The carbonate-bridge of complex14came from the competing reaction ofmethoxy group with N-phenyl benzamide and the succedent CO₂fixation reaction.Copper（Ⅰ） complexes of rigid structure with large conjugation groups usually have good luminescentproperties. In this thesis, nitrogenous ligands of rigid structure with active protonation:₂-phenyl imidazole[4,5-f]1,10phenanthroline （HPIP） ligands were applied to prepare copper（Ⅰ） complex luminescencematerials. Under anhydrous and anoxybiotic conditions, nine neutral （15-₂3） and three ionic copper（Ⅰ）complexes （₂4-₂6） containing bis[₂-（diphenylphosphino）phenyl] ether （DPEphos） or triphenylphosphine（PPh3） main ligand and HPIP ancillary ligands were prepared. The structures of these complexes werecharacterized by IR,1H NMR and X-ray crystallography （15,17,18,19,₂4） methods. The photophysicalproperties of complexes15-26were measured. The results showed that all ionic complexes hardly hasluminescence characters, some neutral complexes emited strong yellow or orange light, and thesubstitution groups of nitrogenous ligands could influence the luminous performances of neutral complexes.All these could provide theoretical basis for the preparation of excellent copper（Ⅰ） complex luminescencematerials.