Mechanisms of organometallic substitution reactions. Part 4. Kinetics of replacement of dimethyl sulphoxide (dmso) from [RuX₂(η-C₆H₆)(dmso)](X = Cl or Br) complexes by triphenylphosphine

Complexes of Ruthenium and Osmium Containing η2–η6 Hydrocarbon Ligands: (iii) Complexes Containing Six-, Seven- and Eight-membered Rings

“…Kinetic studies show that both the slow reaction in DMSO of [RuCl 2 (DMSO)(r|-C 6 H 6 )] with PPh 3 to give [RuCl 2 (PPh 3 )(ri-C 6 H 6 )] and the similar, but faster, reaction in 1,2-dichloroethane proceed via a coordinatively unsaturated intermediate [RuCl 2 (r|-C 6 H 6 )]. 112 Slow crystallization from wet acetone of a mixture of [{RuCl 2 (T|-cym)} 2 ] and Ph 2 PCH 2 SiMe 2 H gives the phosphino-silanol complex [RuCl 2 (PPh 2 CH 2 SiMe 2 OH)(r|-cym)]*, whereas free Ph 2 PCH 2 SiMe 2 H is rapidly cleaved by protic agents to Ph 2 PMe. 113 The diastereomers formed by reaction of (+)-neomenthyldiphenylphosphine with [{RuCl 2 (r|-o-MeC 6 H 4 CO 2 Me)}2] can be separated by fractional crystallization; the less soluble diastereomer has the (R) configuration at the chiral planar unit.…”