Substitution reactions of CpRu (PPh3)2Cl with PPh2H and dppa

Article abstract of DOI:10.1016/S0020-1693(97)05785-X

One PPh₃ group of CpRu(PPh₃)₂Cl is easily substituted by PPh₂H to give the asymmetrical complex CpRu(PPh₃)(PPh₂H)Cl (1) in a very good yield. Attempts to form the λ⁴-phosphanediyl complex CpRu (PPh₃)=PPh₂ (1′) by selective dehydrohalogenation of 1 failed. However, by using one equivalent of the chelating diphosphine dppa two PPh₃ ligands are substituted to yield CpRu(dppa)Cl (2). With an excess of dppa the reaction yielded the N-iminophosphoranyl-substituted dppa complex CpRu{(PPh₂)₂NPPh₂=NH}Cl (3) and PPh₂H. ¹H, ¹³C{¹H} and ³¹P{¹H} NMR, IR and mass spectra of 1-3 are given. Crystals of 1 are monoclinic, space group P2₁/c with a=11.8446(12), b= 14.502(3), c= 17.504(2) A and β=95.55(9)°, Z=4 and R=0.0270 for 4299 observed reflections. Crystals of 2 are monoclinic, space group P2₁/c with a=10.7616(14), b=18.263(4), c= 13.859(2) A and β=110.41(1)°, Z=4 and R=0.0327 for 4227 observed reflections.