phdpa配合物的晶体数据.docVIP

Cu(ClO4)2 induced ortho-benzylation of N-benzyl di(pyridylmethyl)amine and the formation of μ2-Br-bridged copper(II) complexes ) Di(picolyl)amine (dpa) and its derivatives are used as neutral, deprotonated chelating ligands to complex copper(II) atoms to mimic non-heme dioxygenase [1,2]. The reaction of dpa with Cu(ClO4)2 or CuCl2 leads to hexa-coordinated [Cu(dpa)2](ClO4)2 [3] or the mononuclear complex [Cu(dpa)Cl2] [4], respectively, in which the geometry of reported Copper(II)-dpa complexes is a distorted square pyramidal or trigonal bipyramidal. The utility of these ligands is enhanced by the ease with which substituents may be introduced on the imino nitrogen atom, thus resulting the different antitumor activities and catalyzing activities of manganese(II) complexes of dpa and its derivatives [5]. So the synthesis of N-substituted dpa derivatives is meaningful to design functional complexes [6]. Although the intramolecular hydroxylation reaction and the antitumor activities for complexes of N-substituted di(picolyl)amine were extensively studied, there is no report on its intramolecular benzylation [7-9]. Friedel-Crafts reaction of aromatic compounds is one of the important reactions for forming carbon-carbon bonds, as the products serve as useful starting materials for synthesis of pharmaceuticals and materials [10]. They are formed due to replacement of a hydrogen atom of an aromatic compound by a benzyl group derived from benzylating agent in the presence of Lewis acid (e.g. AlCl3, BF3, FeCl3, ZnCl2, etc.) or protonic acids. The copper(I) complexes of (2-pyridyl)alkylamine were reported to activate C-X bond giving C-C bond formation [11]. Copper-containing mesoporous silicas (Cu-HMS-n) and CuCl2 were also widely used as mild, heterogeneous Friedel–Crafts benzylation catalysts [12, 13]. Treatment of [Cu(NCMe)4][PF6] with chelating ligands gave [CuL(NCMe)][PF6] ( L = 9,9-dimethyl-4,5-bis(diphenylphosphino)- xanthene ), which could catalyze the alk