Coinage metal-ethylene complexes of sterically demanding 1,10-phenanthroline ligands.

Phenanthroline-based ligands with bulky aryl groups flanking the metal binding pocket enabled the synthesis and detailed investigation of ethylene complexes of copper(I), silver(I), and gold(I), including structural data of [{2,9-bis(2,4,6-triisopropylphenyl)-1,10-phenanthroline}M(C2H4)][SbF6] (M = Cu, Ag, Au), Additionally, a related copper(I)-ethylene complex with a highly fluorinated ligand is also reported. Gold(I) affects the ethylene moiety significantly as evident from the notable upfield coordination shifts of ethylene carbon signals in the NMR and lengthening of the ethylene CC bond length. Silver(I) forms the weakest bond with ethylene in this series of isoleptic, group 11 metal-ethylene complexes. Preliminary catalytic investigations underscore the potential of copper complexes, particularly those with weakly coordinating supporting ligands, as effective catalysts for C(sp3)-H functionalization through trifluoromethyl carbene insertion.

Synthesis and Investigations of the Antitumor Effects of First-Row Transition Metal(II) Complexes Supported by Two Fluorinated and Non-Fluorinated ß-Diketonates.

The 3d transition metal (Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) complexes, supported by anions of sterically demanding ß-diketones, 1,3-dimesitylpropane-1,3-dione (HLMes) and 1,3-bis(3,5-bis(trifluoromethyl)phenyl)-3-hydroxyprop-2-en-1-one (HLCF3), were synthesized and evaluated for their antitumor activity. To assess the biological effects of substituents on phenyl moieties, we also synthesized and investigated the analogous metal(II) complexes of the anion of the less bulky 1,3-diphenylpropane-1,3-dione (HLPh) ligand. The compounds [Cu(LCF3)2], [Cu(LMes)2] and ([Zn(LMes)2]) were characterized by X-ray crystallography. The [Cu(LCF3)2] crystallizes with an apical molecule of solvent (THF) and features a rare square pyramidal geometry at the Cu(II) center. The copper(II) and zinc(II) complexes of diketonate ligands, derived from the deprotonated 1,3-dimesitylpropane-1,3-dione (HLMes), adopt a square planar or a tetrahedral geometry at the metal, respectively. We evaluated the antitumor properties of the newly synthesized (Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) complexes against a series of human tumor cell lines derived from different solid tumors. Except for iron derivatives, cellular studies revealed noteworthy antitumor properties, even towards cancer cells endowed with poor sensitivity to the reference drug cisplatin.

Synthesis and cytotoxicity studies of Cu(I) and Ag(I) complexes based on sterically hindered ß-diketonates with different degrees of fluorination.

Design, synthesis, and in vitro antitumor properties of Cu(I) and Ag(I) phosphane complexes supported by the anions of sterically hindered ß-diketone ligands, 1,3-dimesitylpropane-1,3-dione (HLMes) and 1,3-bis(3,5-bis(trifluoromethyl)phenyl)-3-hydroxyprop-2-en-1-one (HLCF3) featuring trifluoromethyl or methyl groups on the phenyl moieties have been reported. In order to compare the biological effects of substituents on the phenyl moieties, the analogous copper(I) and silver(I) complexes of the anion of the parent 1,3-diphenylpropane-1,3-dione (HLPh) ligand were also synthesized and included in the study. In the syntheses of the Cu(I) and Ag(I) complexes, the phosphane coligands triphenylphosphine (PPh3) and 1,3,5-triaza-7-phosphaadamantane (PTA) were used to stabilize silver and copper in the +1 oxidation state, preventing the metal ion reduction to Ag(0) or oxidation to Cu(II), respectively. X-ray crystal structures of HLCF3 and the metal adducts [Cu(LCF3)(PPh3)2] and [Ag(LPh)(PPh3)2] are also presented. The antitumor properties of both classes of metal complexes were evaluated against a series of human tumor cell lines derived from different solid tumors, by means of both 2D and 3D cell viability studies. They display noteworthy antitumor properties and are more potent than cisplatin in inhibiting cancer cell growth.