Carboxylato‐Modified New Oxo‐Centred Triruthenium Cluster Compounds with CO and Solvent Ligands: The X‐ray Structure of [Ru₃O(C₂H₅CO₂)₆(CO)(THF)₂]

Abstract

New synthetic precursors for CO‐coordinated, oxo‐centred triruthenium(II,III,III) complexes with varied carboxylato groups [Ru3O(RCO2)6(CO)(solvent)2] where R = C2H5, CH3 and C6H5 have been prepared and characterised. Among the series, the propionato‐bridged complex [Ru3O(C2H5CO2)6(CO)(THF)2] (1) was structurally determined by single‐crystal X‐ray crystallography. Cyclic voltammetry revealed thatthe benzoato‐bridged complex [Ru3O(C6H5CO2)6(CO)(C2H5OH)2] in 0.1 mol dm–3 nBu4NPF6/DMF undergoes two consecutive one‐electron processes assignable to the redox of the Ru3(μ3‐O) core, the redox potentials of which are highly dependent on the electron‐donating/accepting nature of the carboxylato groups. UV‐light excitation of the compounds in CH3CN resulted in the dissociation of CO to form the tris(CH3CN) compounds [Ru3O(RCO2)6(CH3CN)3] (R = C2H5, CH3 and C6H5). These compounds are highly useful as synthetic precursors to a wide range of μ3‐oxo‐triruthenium derivatives with well‐defined redox responses. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Probing the electronic delocalization in a cyclic pyrazine ruthenium cluster hexamer

“…On the other hand, the IC band displays an opposite bathochromic shift. Possibly this is due to a substitution reaction during the hexamer oxidation, since the CO ligand is labile when coordinated to the [Ru 3 O] units in the formal oxidation state +1, [12,13,16] being substituted for solvent molecules such as acetonitrile. In the voltammetry time scale no chemical reaction coupled with the first oxidation process was observed.…”

A pyrazine‐bridged trimer of oxo‐centered triruthenium–carbonyl clusters and the supramolecular assembly built from multiple noncovalent contacts

“…A pyrazine‐bridged trimer of acetate‐bridged triruthenium clusters [Ru 3 O(CH 3 COO) 6 (CO)(pyrazine)] 2 [Ru 3 O(CH 3 COO) 6 (CO)(μ‐pyrazine) 2 ] was first synthesized through multistep processes by Baumann and coworkers. [ 25 ] In the current work, we have prepared a new pyrazine‐bridged trimer 1 (Figure 1) using the propionate‐containing precursor [Ru 3 O(EtCOO) 6 (CO)(THF) 2 ] (THF = tetrahydrofuran) [ 36 ] instead of the acetate analog. Because of the exchangeable ability of the weakly bound THF ligand at the metal center, the [Ru 3 O(EtCOO) 6 (CO)(THF) 2 ] complex is a convenient synthetic precursor for the triruthenium derivatives with various terminal ligands.…”

Solution processing of highly conductive ruthenium and ruthenium oxide thin films from ruthenium–amine complexes

“…The solution was diluted with methanol and CSI-FT-ICR-MS was conducted in a positive ion mode (Fig. 22,23 In addition, inclusion of nitrosyl groups in such trinuclear ruthenium complexes has been observed. The starting Ru material, Ru(NO)(OAc) 3 (m/z = 309), disappeared and the peaks were widely distributed from m/z = 600 to 1600.…”

“…The total structure factors, S(Q) (Fig. 10a were assigned according to the structural data for related ruthenium complexes 23,25 and RuO 2 . 10).…”