Preparation and Properties of Pentafluorosulfanyliminosulfur Difluoride, SF₅N=SF₂

Fluorothiazynes, 50 years old and still exciting: electrophilic attack at the thiazyl nitrogen of NSF2NS(O)F2

“…Surprisingly the structure determination of (-CH 2 -N(CH 3 )SF 2 BN) 2 showed an SN bond distances of 141.2(2) pm [9], even shorter than the distance determined for NSF 3 in the gas phase. As expected the SF bond distance was elongated to 157.5(1) pm from 155.2(3) pm in NSF 3 . This prompted us to investigate the structure of NSF 3 in the solid state (at 120(2) K), for which we determined d(NBS) = 139.9(3) pm and d(SF) = 153.1(3) pm [9].…”

“…From the reaction of S 4 N 4 and AgF 2 almost 50 years ago Glemser and coworkers isolated thiazylfluoride NBSF and thiazyltrifluoride NBSF 3 [1], the first compounds outside carbon chemistry containing nonmetal triple bonds. These two compounds served as starting materials for a vast number of acyclic and cyclic inorganic, organic and organometallic sulfur nitrogen species [2].…”

“…These two compounds served as starting materials for a vast number of acyclic and cyclic inorganic, organic and organometallic sulfur nitrogen species [2]. Only specialists in a few laboratories were able to prepare these compounds [3], their chemistry being investigated by a very limited number of research groups. This might change because Yoshimura et al reported a completely different easy route to diarylfluorothiazynes.…”

“…From the reaction of SS-diaryl-Nbromosulfilimines Ar 2 SNBr and tetra-n-butyl ammonium fluoride [4] and very recently from Ar 2 SNH and Selectfluor [5] they obtained the corresponding diaryl fluoro thiazynes NBS(Ar) 2 F. Similar to NSF 3 the sulfur bonded fluorine is readily exchanged by nucleophiles. Structure determinations of NS(Ar) 2 F and of the products NBSAr 2 R (R = Ph, OPr, NSPh 2 ) showed SN bond distances in the range 144-147 pm [6], not much longer than the SN bond distances reported for NSF 3 in the gas phase (141.6 pm) [7].…”

Reactions of K2[Fe(CO)3(PPh3)]: Reductive Sb−Sb Coupling with Ph2SbCl To Form trans‐[Fe(CO)3(PPh3)(Sb2Ph4)] and Salt Metathesis with Me3SbCl2 To Yield trans‐[Fe(CO)3(PPh3)(SbMe3)]

“…[11] The signal in the 31 P{ 1 H} NMR spectrum of 3 is found at δ ϭ 86.4 ppm. The 1 H and 13 C{ 1 H} NMR spectra show only the multiplets due to the phenyl protons (δ ϭ 7.26Ϫ7.59 ppm) and phenyl-C atoms (δ ϭ 126Ϫ131 ppm), in addition to one signal for the CO ligand (δ ϭ 212 ppm).…”