401900-84-3Relevant academic research and scientific papers
Synthesis and structural characterization of copper(I) and copper(II) complexes with an ambivalent phenanthroline-type ligand
Collin, Jean-Paul,Gavina, Pablo,Sauvage, Jean-Pierre,De Cian, Andre,Fischer, Jean
, p. 951 - 957 (2007/10/03)
The new phenanthroline ligand 2-(p-methoxyphenyl)-9-(5′-methylpyridin-2′-yl)-l,10-phenanthroline L has been synthesized and shown to form four-coordinate CuI (L)2 (1) and six-coordinate CuII(L)2 (2) complexes. Their structures have been determined by X-ray crystallography: (1) C50H38CuN6O2.BF4, triclinic, space group P1, a 12.924(3), b 14.567(4), c 12.649(3) A, α 105-57(2), β 107.68(2), γ 104.00(2)°; (2) C50H38CuN6O2.2PF6, monoclinic, space group P21/c, a 17.701(5), b 19.285(5), c 14.293(4) A, β 98.20(2)°. In solution, cyclic voltammetry measurements indicate for the copper(I) and copper(II) complexes a very fast rearrangement of the pyridine substituent with the change of the oxidation state. Surprisingly, the X-ray data show two different coordination modes for the ligand around the copper(1) ion, the 1,10-phenanthroline nucleus being either mono- or bi-dentate. In solution, since the 1H n.m.r. spectra obtained even at several temperatures display only one set of signals, it is proposed that a fast equilibrium takes place between two coordination modes of the phenanthroline.
Templating and Clipping Coordination Reactions Leading to Heteronuclear Trimetallic Complexes Containing Interlocking Rings
Cardenas, Diego J.,Sauvage, Jean-Pierre
, p. 2777 - 2783 (2008/10/09)
We report the preparation of heterotrimetallic complexes with a Cu-complexed [2]-catenate structure, containing two other metals within the rings. Starting from a multidentate ligand 1 containing two terpy units (terpy 2,2': 6',2 -terpyridine) and one dpp fragment (dpp 2,9-diphenyl-1,10-phenanthroline), a 29-membered macrocycle 2 was prepared in 59% yield by clipping of both terpy moieties of 1 with Ru(DMSO)4Cl2 under high-dilution conditions. Threading of an additional equivalent of ligand 1 through macrocycle 2 was achieved by reaction with Cu(I), which acts as a template, forming a Cu(dpp)2+-type complex bearing two free terpy ligands. Reaction of this complex with different salts of Cu(II), Co(II), Fe(II), and Zn(II) gave the corresponding heteronuclear trimetallic catenates, as mixtures of diastereomers, again by clipping of both terpy units with the metal. The kinetic stability of the Ru complex prevents ligand scrambling. A somewhat different strategy, i.e., simultaneous formation of two rings from Cu(1)2+ by reaction with Ru(DMSO)4Cl2, afforded a catenate containing two Ru(terpy)2+ complexes within the rings. The high stability of these Ru species allows the selective demetalation of Cu(I) to give a catenane containing a free tetrahedral coordination site.
