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The role of the 2,4,6-tris(trifluoromethyl)phenyiamino group in stabilizing new phosphorus-, arsenic-, and germanium-containing main-group compounds and transition-metal derivatives

The reactions of potassium Rf-amide [Rf = tris(trifluoromethyljphenyl] (2) with PCl3, AsCl3, and GeCl2·dioxane yield new four-membered inorganic heterocycles [RfNPCl]2 (3), [RfNAsCl]2 (4), and [RfNGe]2 (5), respectively. On the other hand, the reaction of Rf-amide 2 with two equivalents of RfPCl2 leads to the formation of the imino-λ3-phosphane RfN=PR, (6) and the diamino-λ3-phosphane (RfNH)2PRf (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 coordinates 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 analytical and mass, IR, and NMR (1H, 19F, and 31P) spectroscopy. Further, the molecular structures of all the compounds have been unambiguously determined by single-crystal X-ray diffraction studies. The diazadigermetidine 5 crystallizes in a fluorescent-yellow orthorhombic and a yellow monoclinic crystal modification. The results obtained reveal the role of Rf group in stabilizing new multiple bonded systems and inorganic heterocycles. A skeletal rearrangment of the Rf ligand is observed in the reactions leading to compounds 9 and 10. Moreover, the preparation of compounds 9 and 10 indicates the limitation of the use of this ligand in the preparation of new metal-amide systems, especially where the metal atoms have a strong tendency for the formation of strong M-F bonds. VCH Verlagsgesellschaft mbH.