Programmable multimetallic linear nanoassemblies of ruthenium–DNA conjugates

A new ruthenium–DNA conjugates family was synthesized, made up of a ruthenium complex bound to one or two identical DNA strands of 14–58 nucleotides. The formation of controlled linear nanoassemblies containing one to seven ruthenium complexes is described

Well-defined silica-supported olefin metathesis catalysts

Two triethoxysilyl-functionalized N-heterocyclic carbene ligands have been synthesized and used to prepare the corresponding second-generation ruthenium olefin metathesis catalysts. These complexes were then grafted onto silica gel, and the resulting materials were efficient heterogeneous catalysts for a number of metathesis reactions. The solid-supported catalysts were shown to be recyclable over a number of reaction cycles, and no detectable levels of ruthenium were observed in reaction filtrates (ruthenium concentration of filtrate <5 ppb)

Synthesis, Characterization, and Properties of Mononuclear and Dinuclear Ruthenium(II) Complexes Containing Phenanthroline and Chlorophenanthroline

The study of photophysical and photochemical properties of ruthenium complexes is of great interest for fundamental practical reasons. Ruthenium complexes have been investigated for use in artificial photosynthesis. This paper deals with the synthesis and spectroscopic investigation of custom-designed ruthenium complexes containing phenanthroline and chloro-phenanthroline ligands. These complexes maybe useful for biological electron-transfer studies. The heteroleptic ruthenium monomer complex Ru(phen)2(Cl-phen) (where phen = 1,10-phenanthroline and Cl-phen=5-chloro-1,10-phenanthroline) was prepared in a two-step procedure previously developed in our laboratory. This monomer complex was used to prepare the ruthenium homometallic dimer complex, (phen)2Ru(phen-phen)Ru(phen)2, by utilizing the Ni-catalyzed coupling reaction. Both complexes were purified by extensive column chromatography. The identity and the integrity of the monomer complex were confirmed by elemental analysis. The calculated and the experimental values for the elemental analysis were in good agreement for the monomer complex. UV/Vis absorption spectroscopy, emission spectroscopy, and cyclic voltammetry were used to investigate the properties of both the complexes

Controlling platinum, ruthenium, and osmium reactivity for anticancer drug design

The main task of the medicinal chemist is to design molecules that interact specifically with derailed or degenerating processes in a diseased organism, translating the available knowledge of pathobiochemical and physiological data into chemically useful information and structures. Current knowledge of the biological and chemical processes underlying diseases is vast and rapidly expanding. In particular the unraveling of the genome in combination with, for instance, the rapid development of structural biology has led to an explosion in available information and identification of new targets for chemotherapy. The task of translating this wealth of data into active and selective new drugs is an enormous, but realistic, challenge. It requires knowledge from many different fields, including molecular biology, chemistry, pharmacology, physiology, and medicine and as such requires a truly interdisciplinary approach. Ultimately, the goal is to design molecules that satisfy all the requirements for a candidate drug to function therapeutically. Therapeutic activity can then be achieved by an understanding of and control over structure and reactivity of the candidate drug through molecular manipulation

Functionalisation of bolaamphiphiles with mononuclear bis(2,2'-bipyridyl)ruthenium(II) complexes for application in self assembled monolayers

A novel ruthenium(II) polypyridyl complex connected competently to a bolaamphiphile, containing amide linkages to provide rigidity via hydrogen bonding in the monolayer, has been prepared. The ruthenium(II) complexes of this ligand and of the intermediates in the synthesis were prepared by modification of the coordinated ligands, demonstrating the synthetic versatility and robustness of this family of complexes. All ruthenium complexes were characterised by electrochemical and spectroscopic techniques and were found to have similar properties to the parent complex [Ru(bipy)[3]][2][+], and remain versatile photosensitisers, with well-defined properties, despite extensive substitution of the bipy ligand

The synthesis and characterization of new higher nuclearity arene-ruthenium-sulfur clusters : a thesis presented in partial fulfillment of the requirements for the degree of Master of Science in Chemistry at Massey University, New Zealand

This thesis describes a project investigating the synthesis and characterization of new higher nuclearity arene-ruthenium-sulfur clusters and arene-ruthenium-nitrogen complexes. The thesis is divided into four chapters, with the introduction in Chapter One. The synthesis and characterization of new higher nuclearity arene-ruthenium-sulfur clusters are described in Chapter Two. These include two novel clusters, [Ru₅S₄(cymene)₄](PF₆)₂, [Ru₄(S₂)(SO)(cymene)₄](PF₆)₂ and one known cluster, [Ru₃S₂(cymene)₃](PF₆)₂. The X-ray crystallographic structures of these three arene-ruthenium-sulfur clusters are discussed in detail including how the number of valence electrons influences the structure, how the solid state structure and single crystal structure effect each other and how the structures determine the chemical shifts and other characters of the clusters. The unusual signals of these three clusters on ¹H NMR spectra are discussed carefully. The mechanisms of formation of arene-ruthenium-sulfur clusters are described in detail. Some electrochemistry and calculations (quantum chemistry) are also involved. The synthesis and characterization of arene-ruthenium-nitrogen complexes are described in Chapter Three. These include two new mono-nuclear complexes, [RuCl₂(NH₃)(cymene)], [Ru(NH₃)₃(cymene)](PF₆)₂, one novel amide dimer [RuCl(NH₂)(cymene)]₂ and one known complex, [RuCl(NH₃)₂(cymene)]PF₆. The mechanisms of reactions in which they are formed are also discussed. In Chapter Four, the experimental data is presented. The X ray crystallography of [Ru₅S₄(cymene)₄](PF₆)₂, [Ru₄(S₂)(SO)(cymene)₄](PF₆)₂, [RuCl₂(NH₃)(cymene)] and [RuCl(NH₂)(cymene)]₂ is described in detail

New trends for metal complexes with anticancer activity

Medicinal inorganic chemistry can exploit the unique properties of metal ions for the design of new drugs. This has, for instance, led to the clinical application of chemotherapeutic agents for cancer treatment, such as cisplatin. The use of cisplatin is, however, severely limited by its toxic side-effects. This has spurred chemists to employ different strategies in the development of new metal-based anticancer agents with different mechanisms of action. Recent trends in the field are discussed in this review. These include the more selective delivery and/or activation of cisplatin-related prodrugs and the discovery of new non-covalent interactions with the classical target, DNA. The use of the metal as scaffold rather than reactive centre and the departure from the cisplatin paradigm of activity towards a more targeted, cancer cell-specific approach, a major trend, are discussed as well. All this, together with the observation that some of the new drugs are organometallic complexes, illustrates that exciting times lie ahead for those interested in ‘metals in medicine

(p -Cymene)thioglycollatoruthenium(II) dimer; a complex with an ambi-basic S,O-donor ligand

The title compound was prepared from the (p-cymene)ruthenium chloride dimer and thioglycollic acid. The structure is a centrosymmetric dimer bridged by the soft-base S atoms, with the hard-base O atoms of the carboxylate group chelating to form a five-membered twisted-ring. The coordination of the ruthenium atoms is completed by a η6-p-cymene ligand, giving an 18-electron count. The Ru–S bonds are essentially equal at 2.396(1) Å

Ruthenium polypyridyl complexes and their modes of interaction with DNA : is there a correlation between these interactions and the antitumor activity of the compounds?

Various interaction modes between a group of six ruthenium polypyridyl complexes and DNA have been studied using a number of spectroscopic techniques. Five mononuclear species were selected with formula [Ru(tpy) L1L2](2-n)?, and one closely related dinuclear cation of formula [{Ru(apy)(tpy)}2{l-H2N(CH2)6NH2}]4?. The ligand tpy is 2,20:60,200-terpyridine and the ligand L1 is a bidentate ligand, namely, apy (2,20-azobispyridine), 2-phenylazopyridine, or 2-phenylpyridinylmethylene amine. The ligand L2 is a labile monodentate ligand, being Cl-, H2O, or CH3CN. All six species containing a labile L2 were found to be able to coordinate to the DNA model base 9-ethylguanine by 1H NMR and mass spectrometry. The dinuclear cationic species, which has no positions available for coordination to a DNA base, was studied for comparison purposes. The interactions between a selection of four representative complexes and calf-thymus DNA were studied by circular and linear dichroism. To explore a possible relation between DNA-binding ability and toxicity, all compounds were screened for anticancer activity in a variety of cancer cell lines, showing in some cases an activity which is comparable to that of cisplatin. Comparison of the details of the compound structures, their DNA binding, and their toxicity allows the exploration of structure–activity relationships that might be used to guide optimization of the activity of agents of this class of compounds