Thiazyl trifluoride

Thiazyl trifluoride NSF3 is more thermally stable and easier to handle than NSF (Section 8.3). It can be introduced into transition-metal complexes by SO2 displacement reactions (Eq. 7.8). An alternative route to metal-NSF3 complexes is shown in Eq. 7.9. 

Thiazyl trifluoride, a colourless gas with a pungent odour, is prepared by the oxidative decomposition of FC(0)NSF2 with Agp2 (Eq. 8.5).NSF3 is kinetically very stable even in the liquid form. The chemical inertness of NSF3 resembles that of SFe. For example, it does not react with sodium metal below 200°C. ... 

Only the thiazyl trifluoride can be said to have a single S—F bond within the error limits. The stronger bond in the monofluoride accords with a bond order of 2.4 for S—N estimated from a force constant-distance relationship. The odd-electron molecule NSF2 has the weakest bond. 

Sulfur tetrafluoride undergoes addition to a S = N bond to give hexavalent sulfur tetrafluorides. For example, reaction with thiazyl trifluoride affords a high yield of pentafluoro-X... 

One of the most remarkable molecules is thiazyl trifluoride, NSF (Fig. 18.7). This compound is very stable. It does not react with ammonia at room lemperaiure. with hydrogen chloride even when hented. or with metallic sodium at temperatures below 400 C. The S—N bond. 141.6 pm, is the shortest known between these two elements. The F.SF bond nngle.s of 94° are compatible with approximate j/ bonding and the presence of an rp hybrid cr bond. ind iwo p d n bonds between ihe sulfur and the niirogen. The contraccicr of ihc J orbiuils by the inductive effect of the fluorine atoms presumably permits effective overLip and -jr-bond formation. The alternative explanation would require a double dative bond from the sulfur atom, extremely unlikely in view of the positive character of ihe sulfur atom... 

NFS, Thiazyl fluoride, 24 16 NF2HS, Imidosulfurous difluoride mercury complex, 24 14 NFsOPSiCsHis, Phosphinimidic acid, P,P-dimethyl-iV-(trimethylsilyl)-2,2,2-trifluoroethyI ester, 25 71 NF3OSC, Imidosulfurous difluoride, (fluo-rocarbonyl)-, 24 10 NF3S, Thiazyl trifluoride, 24 12 NFjH, Ammonium, tetrafluoro-, (hydrogen difluoride), 24 43... 

SF3N, Thiazyl trifluoride, 24 12 SF3NOC, Imidosulfurous difluoride, (fluoro-carbonyl)-, 24 10... 

Thiazyl trifluoride (63.8 g 0.619 mol), carbonyl fluoride (51.0 g 0.772 mol) and anhydrous hydrogen fluoride (12.6 g 0.630 mol) are measured out by PVT (pressure, volume, temperature) methods and condensed into a 300-mL stainless steel Hoke cylinder [ISOOpsig (pounds per square inch, gauge)] attached to a stainless steel vacuum line. The cylinder is allowed to warm to room temperature. Then it is placed in a rocker and allowed to shake. 

Thiazyl Trifluoride, NSF3, and Haloiminosulfur Difluorides, XNSF2 (X=F, Cl)... 

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