1 : 2 Adducts of copper(i) halides with 1,2-bis(di-2-pyridylphosphino)ethane: solid state and solution structural studies and antitumour activity

Abstract

The 1 : 2 adducts of copper(I) halides with 1,2-bis(2-pyridylphosphino)ethane (d2pype) have been synthesized and solution properties characterized by variable temperature (1)H, (31)P and (65)Cu NMR spectroscopy. Single-crystal structure determinations for the chloride, bromide and iodide complexes show these to crystallize from acetonitrile in the triclinic space group P1 as isostructural centrosymmetric dimers [(d2pype)Cu(mu-d2pype)(2)Cu(d2pype)]X(2).(solvent) with a approximately 12.6, b approximately 12.7, c approximately 15.3 A, alpha approximately 84, beta approximately 67, gamma approximately 84 degrees. In contrast to the analogous AuCl:2(d2pype) and AgNO(3):2(d2pype) adducts, in solution these CuX:2(d2pype) adducts (where X = Cl, Br and I) exist almost exclusively as bis-chelated monomeric [Cu(d2pype)(2)]X; evidence for an equilibrium between monomeric and dimeric forms is detected only for the CuCl adduct in methanol. Cytotoxicity studies in two human breast cancer lines and two matched liver progenitor cell lines indicate that [Cu(d2pype)(2)]Cl is non selectively toxic to both non-tumourigenic and tumourigenic cells. However, the analogous Au(I) compound [Au(d2pype)(2)]Cl, is toxic to highly tumourigenic cells and more selective in its toxicity to tumourigenic cells compared to non-tumourigenic cells. The significance of these results to the further development of selective, mitochondria-targeted, Au(I) antitumour complexes is discussed.

Synthesis, structure and cytotoxicity studies of four-coordinate bis (cis–bis(diphenylphosphino)ethene) gold(I) complexes, [Au(dppey)2]X

“…Comparison of the M-P bond lengths for these Au complexes with [Cu(dppey) 2 ] + [5,25] and [Ag(dppey) 2 ] + [26,27] complexes shows that the bond lengths increase in the order Cu b Au b Ag in accord with previously established trends [28,29] with average values of 2.282(6), 2.393(13) and 2.484(13) Å respectively.…”

N‐Heterocyclic Carbene–Phosphinidene Complexes of the Coinage Metals

“…[46] As the phosphorus-bridged coppera nd gold complexes 15 and 16 represent related geminally dicuprated or diaurated species, respectively,w ea imed to convert them into cationic and potentially catalytically active complexes by chloridea bstraction. Treatmento fc omplex 15 with one equivalent of sodium tetrakis [(3,5-trifluoromethyl) [32] and we observed ab road signal at À65.4 ppm, which is upfield from the chemical shift that we had observed for complex 15 (d = À53.3 ppm). The compound crystallized as aC H 2 Cl 2 solvate in the triclinic space group P1 ,a nd the asymmetric unit consisted of ad inculear[ (IPr·PPh)Cu 2 Cl)] + moiety,aBAr F ion, and one solventm olecule.…”

“…The absence of such oligomeric or polymeric speciesi nt he solid state has been reported for trinuclear complexes of the type [{(Me 2 N) 2 C·PR}CuCl] 3 (R = Ph, tBu). [31] We proceeded to establisht he molecular structure of the corresponding copper complex 12,w hich showedasimilarly broad signal in the 31 PNMR spectruma tr oom temperature (fwhm = 32 Hz), [32] by X-ray diffractiona nalysiso fi ts tolueneh emisolvate ( Figure 5). The coppera tom exhibits ar arely observed two-coordinate PÀ CuÀCl environment [33] with structuralc haracteristics that are similart ot hose that have been established for the two terminal CuCl moieties in tetrameric [(IMes·PPh)(CuCl) 2 ] 4 , [15] that is PÀCu = 2.1651(6) , CuÀCl = 2.1138(6) , P-Cu-Cl = 166.69(3)8.…”

Structural diversity in dinuclear copper(I) halide complexes of 2,4-dithiouracil: Synthesis, crystal structures, induction of DNA damage and oxidative stress mediated by ROS

“…As a typical example, the electron transfer processes associated with the biological binding, activation and reduction of dioxygen have been found to be mediated by metalloenzymes, the active sites of which consist of dicopper centers [2][3][4][5]. Copper complexes are currently intensively tested for their potential use as antimicrobial [6][7][8] and anti-inflammatory agents [9][10] and for cancer inhibition by chemotherapy [11][12][13][14][15].…”