Spontaneous N-aryl (rather than P-aryl) orthometallation in the system [RuCl2(PPh3)3]–[CN(Ar)(CH2)2NAr]2(Ar = C6H4Me-4); X-ray crystal and molecular structure of [RuCl(PEt3)2{CN(Ar)(CH2)2N(C6H3Me-4)}], a stereochemically rigid 5-co-ordinate RuII complex, with a short (2.2 Å) Ru …. H contact

Abstract

A new type of electron-rich olefin reaction is observed by heating [RuCl₂(PPh₃)₃] in boiling xylene with [[graphic omitted]Ar]₂(Ar = C₆H₄Me-4) to yield the PPh₃ analogue (I) of the title compound (IV)[obtained from (I)+ PEt₃]; the X-ray crystal structure shows that the latter has a significantly shorter Ru–C_carb[1·908(5)Å] than Ru–C_aryl[1·908(5)Å] than Ru–C_aryl[1·994(5)Å] bond, and (IV) and a related compound (III) provide the first examples of stereo-chemically rigid five-co-ordinate Ru^II complexes probably because of an exceptionally close Ru …. H Contact.