Synthesis and structural characterization of the first examples of butadiynyl derived cyclic fluorinated phosphazenes

The first examples of butadiyne derived cyclic fluorophosphazenes have been synthesized and structurally characterized. A reaction of PhC C-C CLi with P3N3F6 yielded the phenylbutadiyne monosubstituted fluorophosphazene, [PhC C-C C(F)PN](PNF2)(2) (1) along with the geminally disubstituted fluorophosphazene [(PhC C-C C)(2)PN](PNF2)(2) (2), while an analogous reaction of FcC C-C C-Li (Fc = ferrocenyl) with N3P3F6 gave the ferrocenylbutiadiyne monosubstituted fluorophosphazene, [FcC C-C C(F)PN](PNF2)(2) (3) and the geminally disubstituted fluorophosphazene [(FcC C-C C)(2)PN](PNF2)(2) (4). Compound 1 on reaction with FcC -CLi yielded the unsymmetrical geminally disubstituted compound [(FcC C)(PhC C-C C)PN](F2PN)(2) (5). Reactions of compound 3 with PhC CLi and FcC CLi, also resulted in unsymmetrically disubstituted fluorophosphazenes [(PhC C)(FcC C-C C)PNI(F2PN)(2) (6) and [(FcC C)(FcC C-C C)PN](F2PN)(2) (7), having both butadiyne and alkyne units on the same phosphorus atom of the heterocycle. All new compounds were characterized by IR, NMR [H-1, C-13{H-1}, P-31{H-1), and F-19{H-1)] and HRMS studies. Compounds 1, 2, 4 and 5 have also been structurally characterized. (C) 2013 Elsevier B.V. All rights reserved.