The Role of the 2,4,6‐Tris(trifluoromethyl)phenylamino Group in Stabilizing New Phosphorus‐, Arsenic‐, and Germanium‐Containing Main‐Group Compounds and Transition‐Metal Derivatives

Abstract

Abstract The reactions of potassium R f ‐amide [R f = tris(trifluoromethyl)phenyl] (2) with PCl 3 , AsC1 3 , and GeC1 2 · dioxane yield new four‐membered inorganic heterocycles [R f NPCl] 2 (3) , [R f NAsC1] 2 (4) , and [R f NGe] 2 (5) , respectively. On the other hand, the reaction of R f ‐amide 2 with two equivalents of R f PCl 2 leads to the formation of the imino‐γ 3 ‐phosphane R f N=PR f (6) and the diamino‐γ3‐phosphane (R f NH)2PR f (7) . The iminophosphane 6 reacts with Ni(CO) 2 (PPh 3 ) 2 and forms the complex [Ni(PPh 3 ) 2 (R f N=PR f )] (9) , in which the imino‐ phosphane coordinates to the metal through the phosphorus lone pair. Treatment of lithium amide 2 with transition metal chlorides ZnCl 2 and FeCl 2 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 ( 1 H, 19 F, and 31 P) 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 R f , group in stabilizing new multiple bonded systems and inorganic heterocycles. A skeletal rearrangment of the R f 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.