Ru(II)‐based antineoplastic: A “wingtip” N‐heterocyclic carbene facilitates access to a new class of organometallics that are cytotoxic to common cancer cell lines

The syntheses, structures, and chemotherapeutic activities of Ag(I)‐, Au(I)‐, and Ru(II)‐complexes ligated to a novel N‐heterocyclic carbene ligand, 2‐(4‐nitrophenyl)imidazo[1,5‐a]pyridin‐2‐ylidene ( 1 ), are described. The corresponding complexes, [Ag( 1 )₂][PF₆], [Au( 1 )₂][PF₆] ( 3 ), and [Ru( 1 )(p‐cymene)Cl][PF₆] ( 4 ), were prepared using convenient transmetallation chemistry and characterized using a range of spectroscopic and analytical techniques. X‐ray crystallography revealed that complexes 2 and 3 adopted linear structures whereas 4 exhibited a prototypical “piano‐stool”‐like geometry; the structural assignments were further supported by DFT calculations. A series of in vitro studies revealed that while the aforementioned Ag(I), Au(I) and Ru(II) complexes exhibited significant cytotoxicities against the human colon adenocarcinoma (HCT 116), lung cancer (A549), and breast cancer (MCF7) cell lines, the Ru derivative was most prominent.     

Synthesis,spectral characterization and redox studies of [1-alkyl-2-(naphthyl-β-azo)imidazole] palladium(II) catecholates

1-Alkyl-2-(naphthyl--azo)imidazoles [-NaiR; R = Me (a), Et (b), CH₂Ph (c)] react with Pd(MeCN)₂Cl₂ to yield Pd(-NaiR)Cl₂ (2), the i.r. spectra of which support the presence of a cis-PdCl₂ configuration. The complexes react with catechols in the presence of Et₃N to yield ternary complexes [Pd(-NaiR)(O,O)] [O,O = pyrocatecholato (cat) (3), 4-t-butylcatecholato (tbcat) (4), 3,5-di-t-butylcatecholato (dtbcat) (5), and tetrachlorocatecholato (tccat) (6)], which were characterized by elemental analysis, i.r. and ¹H-n.m.r. spectral data. Redox studies by cyclic voltammetry suggest the existence of four successive redox couples wherein two responses, positive to s.c.e. are due to catechol to semiquinone and semiquinone to quinone oxidation, respectively; the couples at negative to s.c.e. are referred to azo reductions. The complexes exhibit ligand-ligand charge-transfer transitions in the near-i.r. region. The band position is largely dependent upon the substitutent on the catechol frame and exhibits negative solvatochromic effects. The transition is qualitatively assigned as the HOMO (cat) LUMO (-NaiR) transition. This fact is also supported by theoretical calculations using the PM3 method.     

Naphthyl-(2-pyridylmethylene)amine complexes of silver(I) and ruthenium(II): synthesis,spectral studies and electrochemical behaviour

Pyridine-2-carboxaldehyde reacts with /-naphthylamine to give /-naphthyl-(2-pyridylmethylene)amine [-L (1), -L (2)]. L belongs to the unsymmetric diimine (—N=C—C=N—) family which can form five–membered chelate rings with metal ions. {donor centers are abbreviated as N[N(Py)] and N [N(nap)]} [Ag(L)₂]⁺ complexes were prepared and characterized by spectroscopic data. The reaction between L and RuCl₃ in boiling EtOH yielded green and blue–green compounds of composition RuCl₂(L)₂. I.r., u.v.–vis. and ¹H-n.m.r. data determined the stereochemistry of the complexes as trans-cis-cis (green) and cis-trans-cis (blue–green) according to the sequence of the coordination pair of Cl, N [N(Py)] and N [N(nap)]. Upon treatment of Ag(L)₂ ⁺ with Ru(bpy)₂Cl₂ in alcoholic suspension the ternary complexes, [Ru(bpy)₂(L)](ClO₄)₂, were isolated and characterized by spectroscopic data. [Ru(bpy)(L)₂](ClO₄)₂ complexes were synthesized similarly from ctc-Ru(L)₂Cl₂ and 2,2-bipyridine (bpy) in the presence of AgNO₃ and NaClO₄. These complexes show well-defined m.l.c.t transitions in the visible region. The sterochemistry of the complexes was established by ¹H-n.m.r. data. Cyclic voltammetry shows a high potential Ru^III/Ru^II couple and follows the order: [Ru(bpy)(L)₂]²⁺ > [Ru(bpy)₂(L)]²⁺ > Ru(-L)₂Cl₂ > Ru(-L)₂Cl₂.     

Synthesis,X-ray crystal structure,DFT calculations,spectroscopic characterization and redox behaviour of a rhodium(III) complex of an anthracene–pyridylhydrazone ligand

Transition Metal Chemistry - A pyridylhydrazone incorporating an anthracene moiety, designated as HLAnc, has been synthesized in order to examine its coordination behaviour towards rhodium(III)....     

Anion Storage Chemistry of Organic Cathodes for High-Energy and High-Power Density Divalent Metal Batteries

Multivalent batteries show promising prospects for next-generation sustainable energy storage applications. Herein, we report a polytriphenylamine (PTPAn) composite cathode capable of highly reversible storage of tetrakis(hexafluoroisopropyloxy) borate [B(hfip)₄] anions in both Magnesium (Mg) and calcium (Ca) battery systems. Spectroscopic and computational studies reveal the redox reaction mechanism of the PTPAn cathode material. The Mg and Ca cells exhibit a cell voltage >3 V, a high-power density of ∼∼3000 W kg⁻¹ and a high-energy density of ∼∼300 Wh kg⁻¹, respectively. Moreover, the combination of the PTPAn cathode with a calcium-tin (Ca−Sn) alloy anode could enable a long battery-life of 3000 cycles with a capacity retention of 60 %. The anion storage chemistry associated with dual-ion electrochemical concept demonstrates a new feasible pathway towards high-performance divalent ion batteries.     

Solution study of a structurally characterized monoalkoxo-bound monooxo-vanadium(V) complex: spontaneous generation of the corresponding oxobridged divanadium(V,V) complex and its electroreduction to a mixed-valence species in solution

An interesting transformation of a structurally characterized monooxoalkoxovanadium(V) complex [VO(OEt)L] (LH 2 = a dibasic tridentate ONO donor ligand) in solution leading to the formation of the corresponding monooxobridged divanadium(V,V) complex (VOL) 2O is reported. This binuclear species in solution is adequately characterized by elemental analysis, measurement of conductance (in solution), various spectroscopic (UV-vis, IR, NMR, and mass spectrometry) techiniques and by cyclic voltammetry. The corresponding mixed-valence vanadium(IV,V) species has been generated in CH 3CN solution by controlled potential electrolysis of (VOL) 2O. This mixed-valence species is identified and studied by EPR technique (at room temperature and at liquid nitrogen temperature) and also by UV-vis spectroscopy. This study may be regarded as a general method of obtaining monooxo-bridged binuclear vanadium(V,V) species from the corresponding mononuclear monooxoalkoxovanadium(V) complexes of some selected dibasic tridentate ONO chelating ligands, which can be utilized as the precursor of monooxobridged divanadium(IV,V) mixed-valence species in solution obtainable by controlled potential electrolysis.     

Naturally occurring iridoids and secoiridoids. An updated review, part 4

A compilation of new naturally occurring iridoids and secoiridoids including their glycosides, esters, aglycones, derivatives and dimers reported during mid 2008-2010 is provided with available physical and spectral data: mp, [α](D), UV, IR, circular dichroism (CD), (1)H- and (13)C-NMR as well as natural source with family and references. The important bioactivity of new and known iridoids and secoiridoids reported during this period is also highlighted.     

Redox-active ionic-liquid-assisted one-step general method for preparing gold nanoparticle thin films: applications in refractive index sensing and catalysis

We describe a general one-step facile method for depositing gold nanoparticle (GNP) thin films onto any type of substrates by the in situ reduction of AuCl(3) using a newly designed redox-active ionic liquid (IL), tetrabutylphosphonium citrate ([TBP][Ci]). Various substrates such as positively charged glass, negatively charged glass/quartz, neutral hydrophobic glass, polypropylene, polystyrene, plain paper, and cellophane paper are successfully coated with a thin film of GNPs. This IL ([TBP][Ci]) is prepared by the simple neutralization of tetrabutylphosphonium hydroxide with citric acid. We also demonstrate that the [TBP][Ci] ionic liquid can be successfully used to generate GNPs in an aqueous colloidal suspension in situ. The deposited GNP thin films on various surfaces are made up of mostly discrete spherical GNPs that are well distributed throughout the film, as confirmed by field-emission scanning electron microscopy. However, it seems that some GNPs are arranged to form arrays depending on the nature of surface. We also characterize these GNP thin films via UV-vis spectroscopy and X-ray diffractometry. The as-formed GNP thin films show excellent stability toward solvent washing. We demonstrate that the thin film of GNPs on a glass/quartz surface can be successfully used as a refractive index (RI) sensor for different polar and nonpolar organic solvents. The as-formed GNP thin films on different surfaces show excellent catalytic activity in the borohydride reduction of p-nitrophenol.