Gemischtligand-Komplexe des Rheniums. IV. Die Reaktion von [ReNCl2(Me2PhP)3] mit Dithiocarbamaten. Kristallstrukturen von trans-Chloro-dimethyldithiocarbamato-bis(dimethylphenylphosphan) nitridorhenium(V), [ReN(Cl)(Me2PhP)2(Me2dtc)], und Bis(diethyldithiocarbamato)(dimethylphenylphosphan)nitridorhenium(V), [ReN(Me2PhP)(Et2dtc)2]

Mixed-Ligand Complexes of Rhenium IV. The Reaction of [ReNCl₂(Me₂PhP)₃] with Dithiocarbamates. X-Ray Crystal Structures of trans-Chloro-dimethyldithiocarbamato-bis(dimethylphenylphosphine) nitridorhenium(V), [ReN(Cl)(Me₂PhP)₂(Me₂dtc)], and Bis(diethyldithiocarbamato)(dimethylphenylphosphine)nitridorhenium(V), [ReN(Cl)(Me₂PhP)(Et₂dtc)₂] [ReNCl₂(Me₂PhP)₃] reacts with dialkyldithiocarbamates, R₂dtc^?, under a stepwise ligand exchange. Final products of these reactions are the well-known [ReN(R₂dtc)₂] bischelates. Intermediatelly, however, complexes of the general formulae [ReN(Cl)(Me₂PhP)₂(R₂dtc)] and [ReN(Me₂PhP)(R₂dtc)₂] can be isolated. Representatives have been structurally characterized. [ReN(Cl)(Me₂PhP)₂(Me₂dtc)] crystallizes monoclinic in the space group P2₁/c, Z = 4. The dimensions of the unit cell are a = 13.071(3); b = 11.622(1); c = 15.667(3) Å; β = 97.09(1)°. The rhenium atom has a distorted octahedral environment; the Re≡N bond length is 1.71(1) Å. The Re? Cl bond distance is markedly lengthened (2.665(2) Å) as a consequence of the strong trans labilizing influence of the coordinated nitrido ligand. [ReN(Me₂PhP)(Et₂dtc)₂] crystallizes monoclinic in the space group P2₁/c, Z = 4, a = 17.262(3); b = 14.915(2); c = 9.888(2); β = 76.35(8)°. The equatorial coordination sphere is occupied by one phosphorus atom and three sulphur atoms. One of the dithiocarbamate ligands is coordinated bidentately; the second one with two distinct Re? S bond lengths. The Re? S(4) distance is 2.7983(2) Å which can be discussed as a weak interaction with the metal.