Solid- and gas-phase structures and spectroscopic and chemical properties of tris(pentafluorosulfanyl)amine, N(SF 5 ) 3 , and bis(pentafluorosufanyl)aminyl radical, N(SF 5 ) 2
2017
Abstract Tris(pentafluorosulfanyl)amine, N(SF 5 ) 3 , and the bis(pentafluorosulfanyl)aminyl radical, N(SF 5 ) 2, have been synthesized and characterized by gas electron diffraction, single crystal XRD, NMR, EPR, FT-IR, Raman, and UV–vis spectroscopy, and by their thermal decompositions. The amine possesses a planar molecular structure of D 3 symmetry with an unusually long N S bond of 1.829(6) A. The long N S bonds are in accordance with the small Arrhenius activation barrier for the decay into N(SF 5 ) 2 and SF 5 radicals of 6.9 kcal mol −1 , and its half-life at room temperature is only 50 min. The aminyl radical possesses C 2 symmetry with N S = 1.692(4) A and S N S = 135.1(5)°, and its structure is similar to that of FN(SF 5 ) 2 . This radical is much more stable than the amine (half-life at room temperature is 130 min). Dimerization and formation of the corresponding hydrazine, (SF 5 ) 2 NN(SF 5 ) 2 , was not observed, nor was the nitrene:NSF 5 or its isomer FN SF 4 .
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