Synthese, Strukturen, Ligandenaustauschreaktionen und Elektrochemisches Verhalten der Nitrilkomplexe cis-[Ru(dppm)2Cl(NCR)]+ PF6– (dppm = Bis(diphenylphosphino)methan, R = CH3, C2H5, tBu, Ph)

Isomerically pure nitrile complexes cis-[Ru(dppm)2Cl(NCR)]+ (2 a–d) are formed upon chloride displacement from cis-[Ru(dppm)2Cl2] (1) or, alternatively, by ligand substitution from the acetonitrile complex 2 a. This latter approach does also allow for the introduction of pyridine (3 a,b), heptamethyldisilazane (4) or isonitrile ligands (5). All complexes are obtained as the configurationally stable cis-isomers. Only cis-[Ru(dppm)2Cl(CNtBu)]+ slowly isomerizes to the trans from. The solid state structures of the CH3CN, C2H5CN and the trans-tBuNC complexes were established by X-ray crystallography. Electrochemical investigations of the nitrile complexes 2 a–d show in addition to a chemically reversible one-electron oxidation an irrversible reduction step. In CH2Cl2 solution, cis- and trans-[Ru(dppm)2Cl2] have been identified as the final products of the electrochemically induced reaction sequence