13840-74-9Relevant academic research and scientific papers
Sulfinylimines: Important building blocks for developing the polysulfanemono-and -disulfonic acid chemistry
Boese, Roland,Graw, Michael,Haas, Alois,Krueger, Carl,Moenicke, Annett,Schlagheck, Jens
, p. 1261 - 1272 (2008/10/08)
Besides hydrolysis of perfluoroorganosulfanesulfinylimines in closed systems, reactions of RfSxCl with K2S2O5 or M2S2O3 are also productive methods for the preparation of perfluoroorganosulfanemonosulfonates. The free acid CF3SSSO3H is made by treating the potassium salt with a strong acidic cation resin. It is unstable and shows a pKs-value of approx. -0,5 providing an acidity comparable with polyphosphoric acids. Metathetical reactions of the potassium salts with [(C6H5)4M]Cl (M = P, As) or [R4N][ClO4] (R = n-C3H7) n-C4H9) respectively lead to well crystallized salts. Single crystals are used for x-ray structure analysis. These prove the polysulfanesulfon-moiety to be present in these molecules. Sulfur-sulfur-bonds can also be evidenced by chlorolysis reactions. Not only with Cl2 but also with SCl2 RfSxCl or RfSx+1Cl and ClSO2OM are formed respectively. In this way CF3SSSCl is prepared for the first time. The reaction of CF3SeBr and K2S2O5 provides K[CF3SeSO3] which is unstable and decomposes to CF3SeSeCF3, K2S2O6, SO2 and KBr. When S2Cl2 is reacted with (CH3)3SiNSO besides the main product S2(NSO)2 also minor amounts of Sx(NSO)2 (x = 3, 4, 5) are formed. While hydrolysis of S2(NSO)2 leads quantitively to (NH4)2S4O6, a mixture of ammoniumpolysulfanedisulfonates are obtained from Sx(NSO)2 which could not be separated. It is demonstrated that chemical reactivity is dominated by disproportionation of S2(NSO)2 into S(NSO)2 and sulfur. Additonal sulfinylimines are obtained by metathesis of XNSO (X = Cl, Br) and AgSCN or AgSeCN respectively. The structures of S2(NSO)2 and OSNSCN are established by x-ray methods. By spectroscopical evidence it is shown that OSNSeCN is isostructured with OSNSCN.
Reactions of the trisulfur trinitride anion, S3N3-, with halogens and other electrophilic substrates
Chivers, Tristram,Rao, M. N. Shudheendra
, p. 1957 - 1962 (2007/10/02)
The reactions of the trisulfur trinitride anion, S3N3-, with halogens (Cl2, Br2, I2), AsF5, SOCl2, SO2Cl2, S2Cl2, COCl2, CS2, Me3SiCl, and Ph2PCl have been investigated.In all cases these reactions gave mixtures of known sulfur-nitrogen compounds.Thus the halogens react with S3N3- to give mainly S4N4, S4N3+X- (X=Br, Cl), (SN)x, and S3N3X3 (X=Cl), while AsF5 oxidizes S3N3- to S4N4*AsF5.The major products of the reaction of S3N3- with SOCl2 or SO2Cl2 were S4N4, S4N3+Cl-, and (for SOCl2 only) S3N2O2.S3N2Cl was the main product of the reaction of S3N3- with S2Cl2, whereas COCl2 yielded (SN)x in addition to S3N2Cl and S4N4.Carbon disulfide reacts with S3N3- to give S4N2, S4N4, and CNS-.The cyclophosphathiazenes, (Ph2PN)(SN)2, 1,3- and 1,5-(Ph2PN)2(SN)2, in addition to (Ph2PN)x (x=3, 4), (Ph2PN)3*HCl and (Ph2PN)2NSCl were isolated from the reactions of Ph2PCl with S3N3- in various molar ratios.The latter reaction represents a useful alternative synthesis of the 1,5-isomer of the eight-membered ring (Ph2PN)2(SN)2.
THE REDETERMINATION OF THE STRUCTURE OF TRISULPHUR DINITROGEN DIOXIDE
MacLean, Greg,Passmore, Jack,White, Peter S.,Banister, Arthur,Durrant, James A.
, p. 187 - 190 (2007/10/02)
The crystal structure of S3N2O2 has been redetermined and the structure refined to a final R of 0.057 and Rw of 0.076 for 550 reflections with I>/=2?(I).S3N2O2 is planar and of C2ν symmetry; as previously found by Weiss.The central S-N distances and angle are 1.647(3) Angstroem, NSN 97.3(2) deg, with adjacent N-S distances and angles of 1.535(3) Angstroem, SNS 124.3(2) deg , and terminal S-O distances and angles of 1.446(4) Angstroem, NSO 118.0(2) deg.The infrared and Raman spectra are reported and some assignments are made.
