New Aspects of the Reaction of Difluorosulfur Imides with Fluorine

Abstract

A good entry to the highly reactive fluorine compound (2) is provided by reaction of (1) with fluorine in Pyrex vessels with UV irradiation. In metal autoclaves, (3), (4), and other products are obtained (R = C2F5) without irradiation.

Solid-State and Solution Rearrangements of F3S≡NXeF+Leading to the F4S═NXe+Cation; Syntheses, HF Solvolyses, and Structural Characterizations of [F4S═NXe][AsF6] and [F4S═NH2][AsF6]

“…7 Until the present study, the only species bonded to sp 2 -hybridized nitrogen atoms of inorganic ligands were those derived from the imidobis(sulfurylfluoride) group and included FXeN(SO 2 F) 2 , [8][9][10] Xe[N(SO 2 F) 2 ] 2 , 9,11 9,11,12 and XeN(SO 2 F) 2 + , 12 as well as the related imidobis(sulfuryltrifluoromethyl) group, which is solely represented by Xe[N(SO 2 CF 3 ) 2 ] 2 . 13 Species containing the F 4 SdN-group are presently limited to the neutral molecules F 4 SdNL (L ) F, [14][15][16][17] CH 2 CH 3 , 20 CF 3 , [22][23][24] CF 2 CF 3 , 25 SF 5 , [26][27][28] SO 2 F, 29,30 and C(O)N(CH 2 CH 3 ) 2 31 ) and F 4 SdN • . 32 The majority have been characterized by vibrational 14,18,20,22,25,26,29,31 and NMR 15,[18][19][20][23][24][25][26]29,31 spectroscopy, and a number have been characterized by electron diffraction…”

“…13 Species containing the F 4 SdN-group are presently limited to the neutral molecules F 4 SdNL (L ) F, [14][15][16][17] CH 2 CH 3 , 20 CF 3 , [22][23][24] CF 2 CF 3 , 25 SF 5 , [26][27][28] SO 2 F, 29,30 and C(O)N(CH 2 CH 3 ) 2 31 ) and F 4 SdN • . 32 The majority have been characterized by vibrational 14,18,20,22,25,26,29,31 and NMR 15,[18][19][20][23][24][25][26]29,31 spectroscopy, and a number have been characterized by electron diffraction 14,19 and microwave spectroscopy. 14,19 Solvolysis of NtSF 3 in anhydrous HF (aHF) occurs by the addition of two molecules of HF across the sulfur-nitrogen triple bond to give the primary amine, F 5 SNH 2 , 33 whereas solvolysis of NtSF 3 in the superacid medium, AsF 5 /aHF, results in amine protonation to give [F 5 SNH 3 ][AsF 6 ].…”

Chemistry of Thiazyl Fluoride (NSF) and Thiazyl Trifluoride (NSF3): A Quarter Century of Sulfur‐Nitrogen‐Fluorine Chemistry

“…The silver salt reacts in quite a different way with organometallic halides'1931 [Reaction (74)], the cation Me3M@ is bound to an 0 atom of the anion. The "F-NMR spectrum o * ,OMMe3…”

CH3N=SF2=NCH3: Structural, Conformational, and Configurational Properties in the Gaseous and in the Condensed Phases

“…In addition to the products obtained from the direct fluorination, R–N=SOF 2 was isolated in reasonable yields 23. If the reaction is carefully followed (e.g., by IR spectroscopy), even R f –N=SF 4 (R f = C 2 F 5 , i C 3 F 7 ) can be isolated 24. (see Scheme , B).…”