Spontaneous N-aryl (rather than P-aryl) orthometallation in the system [RuCl 2 (PPh 3 ) 3 ]–[CN(Ar)(CH 2 ) 2 NAr] 2 (Ar = C 6 H 4 Me-4); X-ray crystal and molecular structure of [RuCl(PEt 3 ) 2 {CN(Ar)(CH 2 ) 2 N(C 6 H 3 Me-4)}], a stereochemically rigid 5-co-ordinate Ru II complex, with a short (2.2 Å) Ru …. H contact

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–Ccarb[1·908(5)Å] than Ru–Caryl[1·908(5)Å] than Ru–Caryl[1·994(5)Å] bond, and (IV) and a related compound (III) provide the first examples of stereo-chemically rigid five-co-ordinate RuII complexes probably because of an exceptionally close Ru …. H Contact.