The reaction of [Re(NR)Cl3(PPh3)2] (R = Me or p-MeC6H4) with salicylaldehyde (SalH) gives rise to new rhenium nitrene (imido) complexes [Re(NR)Cl2(Sal)PPh3]. The corresponding PMe2Ph derivatives cis- and trans-[Re(NMe)Cl3(PMe2Ph)2] and trans-[Re(NTo)Cl3(PMe2Ph)2] (To =p-MeC6H4) do not react with SalH or SalLi under the same experimental conditions. By reaction of [Re(NTo)Cl2- (Sal)PPh3] with PR3 (PR3=PMe2Ph, PEt2Ph, PEt3, or PMePh2) the complexes [Re(NTo)Cl2(CHOSal)(PR3)2] are obtained, in which the ligand is monodentate. Reaction of [Re(NTo)Cl2(CHOSal)(PMe2Ph)2] with p-toluidine, gives the Schiff base derivative [Re(NTo)Cl2(S.B.)(PMe2Ph)]. The crystal structure of the title compound was determined by x-ray crystallography. The compound is triclinic, space group PI, with a=11.698(5), b=11.445(5), c=11.725(5) Å, α= 74.12(3)°, β=102.65(3)°, γ=86.89(3)°; Dx=1.69 g cm-3 for Z=2. The structure was refined to R=0.058 for 4400 observed reflections. The rhenium atom is in a distorted octahedral coordination with the chlorine atoms trans to each other. Relevant bond lengths are: Re-Cl, 2.381(3) and 2.424(3) Å; Re-P, 2.427(3) Å; Re-O, 2,01(1) and 2.08(1) Å; Re-N, 1.72(1) Å. © 1984 Verlag Chemie GmbH.
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