Ruthenium-catalyzed Atom Transfer Radical Addition Reactions

Certain ruthenium complexes are potent catalysts for atom transfer radical addition (ATRA) and cyclization (ATRC) reactions, in particular if they are used in conjunction with reducing agents such as magnesium. This short overview summarizes recent developments in this area with special focus on contributions from our laboratory

Research in the Laboratory of Supramolecular Chemistry: Functional Nanostructures, Sensors, and Catalysts

This article summarizes research activities in the Laboratory of Supramolecular Chemistry (LCS) at the EPFL. Three topics will be discussed: a) the construction of functional nanostructures by multicomponent self-assembly processes, b) the development of chemosensors using specific receptors or ensembles of cross-reactive sensors, and c) the investigation of novel synthetic procedures with organometallic catalysts

Functionalised Clathrochelate Complexes – New Building Blocks for Supramolecular Structures

Tris(dioxime) iron(II) clathrochelate complexes functionalised with 3- and 4-pyridyl groups have been employed as building blocks in the preparation of supramolecular structures by coordination-driven self-assembly. These complexes possess a number of desirable characteristics, being straightforward to synthesise and offering ample opportunity for steric and functional modification. Clathrochelate-based 4,4'-bipyridyl metalloligands from 1.5 nm to 5.4 nm in length were prepared in up to two steps and their potential as building blocks for supramolecular architectures demonstrated through the preparation of a discrete molecular square and a three dimensional (3D) coordination polymer. Furthermore, the structure-directing capability of clathrochelate building blocks was illustrated through the synthesis of octahedral cage compounds, which are capable of encapsulating the large, hydrophobic BPh4– anion in aqueous solvent mixtures

Pattern-Based Sensing of Nucleotides in Aqueous Solution with a Multicomponent Indicator Displacement Assay

A multicomponent indicator displacement assay ( MIDA) based on an organometallic receptor and three dyes can be used for the identification and quantification of nucleotides in aqueous solution at neutral pH

Sensing with Dynamic Combinatorial Libraries of Metal-Dye Complexes: The Advantage of Time-Resolved Measurements

A dynamic combinatorial library of metal–dye complexes was obtained by reacting aqueous solutions of the dyes Methyl Calcein Blue, Arsenazo I, and Xylenol Orange with CuCl2 and NiCl2. The mixture gave a characteristic UV-Vis response upon addition of the peptide hormones angiotensin I and angiotensin II. This allowed distinguishing pure samples of peptide hormones from mixtures. The discriminatory power of the sensor was enhanced when the several UV/Vis measurements were performed during the equilibration process of the library

Sequential ATRA-Reductive Cyclopropanation Reactions with a Ruthenium Catalyst in the Presence of Manganese

Atom-transfer radical addition (ATRA) reactions of ethyl trichloroacetate, dichloromalononitrile, or diethyl 2,2-dichloromalonate with olefins followed by dechlorination have provided functionalized cyclopropanes in one step. The RuIII complex [Cp*RuCl2(PPh3)] was used as a catalyst precursor and commercial Mn powder as reducing agent. Reactions with the less activated substrate ethyl dichloroacetate gave ATRA products with high turnover numbers but cyclopropanation was not observed