THE ROLE OF THE 2,4,6-TRIS(TRIFLUOROMETHYL)PHENYLAMINO GROUP IN STABILIZING NEW PHOSPHORUS-CONTAINING, ARSENIC-CONTAINING, AND GERMANIUM-CONTAINING MAIN-GROUP COMPOUNDS AND TRANSITION-METAL DERIVATIVES

The reactions of potassium R-f-amide [R-f=tris(trifluoromethyl)phenyl] (2) with PCl3, AsCl3, and GeCl2 . dioxane yield new four-membered ino rganic heterocycles [RfNPCl](2) (3), [RfNAsCl](2) (4), and [RfNGe](2) (5), respectively. On the other hand, the reaction of R-f-amide 2 with two equivalents of RfPCl2 leads to the formation of the imino-lambda( 3)-phosphane RfN=PRf (6) and the diamino-lambda 3-phosphane (RfNH)(2)P Rf (7). The iminophosphane 6 reacts with Ni(CO)(2)(PPh3)(2) and forms the complex [Ni(PPh3)(2)(RfN=PRf)] (9), in which the iminophosphane co ordinates to the metal through the phosphorus lone pair. Treatment of Lithium amide 2 with transition metal chlorides ZnCl2 and FeCl2 yields the imido/amido spirocyclic metal derivatives 9 and 10, respectively. Compounds 3-10 have been extensively characterized by their analytica l and mass, IR, and NMR (H-1, F-19, and P-31) spectroscopy. Further, t he molecular structures of all the compounds have been unambiguously d etermined by single-crystal X-ray diffraction studies. The diazadigerm etidine 5 crystallizes in a fluorescent-yellow orthorhombic and a yell ow monoclinic crystal modification. The results obtained reveal the ro le of R-f group in stabilizing new multiple bonded systems and inorgan ic heterocycles. A skeletal rearrangment of the R-f ligand is observed in the reactions leading to compounds 9 and 10. Moreover, the prepara tion of compounds 9 and 10 indicates the limitation of the use of this ligand in the preparation of new metal-amide systems, especially wher e the metal atoms have a strong tendency for the formation of strong M -F bonds.