Tethering versus Non‐Coordination of Hydroxy and Methoxy Side Chains in Arene Half Sandwich Dichloro Ruthenium Complexes

We are reporting on the hydroxyalkyl appended arene ruthenium half sandwich complexes [{η6‐C6H5(CH2)nOH}RuCl2] (n = 2, 3) and the methyl ether of the hydroxypropyl derivative. Most significantly, a structural comparison between the hydroxypropyl complex 1a and its methyl ether 2a reveals, that the latter adopts the conventional dichloro bridged dimeric structure while 1a is a monomer. Coordinative saturation of the ruthenium centre is achieved by intramolecular coordination of the appended hydroxy function, thus rendering the functionalized arene an eight electron donor chelate ligand. The structure is further stabilized by intermolecular OH···Cl hydrogen bridges between a terminal chloride ligand of one and the coordinated hydroxy group of a neighbour molecule, resulting in a sheet structure. These intermolecular interactions appear to be even stronger in the hydroxyethyl analogue. Several phosphine adducts have been prepared from the hydroxy or alkoxy functionalized [(η6‐arene)RuCl2]n precursors, including water soluble P(CH2OH)3 adducts. Electrochemical properties of the phosphine adducts and of the dichloro bridged aryl ether complex 2a are also discussed.