The crystal structures of three compounds containing eight-membered Si4(N,O)4 rings have been determined: [t-Bu2SiOSiMe2O]2 (I), [t-Bu2SiOSiMe2NH]2 (II) and [i-Pr2SiNH]4 (III). I forms monoclinic crystals, space group C2/c, with a 14.124(4), b 13.191(4), c 16.156(6) Å, β 108.09(2)°, Z = 4. II also crystallizes in C2/c, with a 14.234(5), b 13.372(6), c) 16.142(8) Å, β 108.87(3)°, Z = 4. The structure determinations show that I and II are essentially isostructural, with effectively planar eight-membered rings lying on crystallographic inversion centres. However the SiOSi angle in II is almost linear (178.0(1)°) and the SiNSi angle is 145.2(2)°, whereas intermediate values are observed for the SiOSi angles in I (156.0(1), 164.2(1)°). III is tetragonal, space group I4, with a, b 13.722(1), c 8.911(2) Å, Z = 2. The ring adopts a tub conformation with SiNSi 139.1(2)°, and the molecule possesses crystallographic S4(4) symmetry. The structures were refined to R = 0.039, 0.053, and 0.040 for 2285, 2081, 696 unique observed reflections, respectively.

Abstract1,il‐Silylgruppenwanderung am Si3CSiO‐Gerüst.

AbstractDie bei aufgezeichneter, 1:1‐molarer Reaktion gebildete, achtgliedrige cyclische Titelverbindung (III) disproportioniert in Toluol bei milden Bedingungen unter Bildung des P(V)‐Dimeren (IV).

Abstract The nature of the products which are formed in the reaction of tris(trimethylsilyl)Methylfluorosilanes (Me3Si)3C -SiF2R with KOH depends on the bulkiness of the substituents R. The condensed siloxane is obtained for R = F . The crystal structure determination of this siloxane (Me3Si)3C -SiF2-O -SiF2-C (SiMe3)3 shows that the Si -O - Si unit is linear. A fluorosilanol as well as a siloxane could be isolated for R = Me. 1,3-Migration of one or two trimethylsilyl groups from the carbon to the oxygen takes place for R = phenyl, rm-butyl or silylamine, with formation of siloxanes which are isomeres o f the expected silanols.

AbstractDie 1:1‐molare Umsetzung des P‐dichlorids (I) mit Bis‐[trimethylzinnl‐sulfid (II) ergibt die Titelverbindung (III), die mit elementarem Schwefel zu der Vierringverbindung (IV) reagiert.

The 1 : 1 reaction between PPhCl2 and (SnMe3)2S in CS2 provides a convenient direct route to (PhP)3S3(1), which reacts with elemental sulphur to give (PhP)2S4(2). Both structures have been determined by X-ray diffraction using twinned crystals. Compound (1) is monoclinic, space group P21, with a= 8.884(2), b= 13.713(2), c= 8.309(2)Å, β= 106.61 (2)°, Z= 2, and R= 0.051 for 1 938 unique observed reflections. The structure contains an unsymmetrical five-membered ring with one exocyclic sulphur, and does not agree with a previous proposal based on n.m.r. data. Compound (2) is monoclinic, space group P21/c, with a= 6.624(1), b= 14.438(3), c= 7.667(2)Å, β= 95.31(2)°, Z= 2, and R= 0.060 for 880 unique observed reflections. The four-membered ring with two trans exocyclic sulphurs possesses a crystallographic centre of symmetry.

The 1:1 reaction between PRCl2(R = C6H2Me3-2,4,6) and (Me3Si)2S in toluene yields (RPS)4(1) which slowly disproportionates under mild conditions (35–40 °C, 3 d) to (RPS2)2(2). Both structures have been determined by X-ray diffraction. Compound (1) is monoclinic, space group Cc, with a= 2 299.3(7), b= 1 167.9(3), c= 1 937.8(6) pm, β= 130.65(2)°, and Z= 4; R= 0.050 for 3 209 unique observed reflections. The eight-membered (PS)4 ring adopts the crown conformation but is disordered. Compound (2) is monoclinic, space group P21/c, with a= 890.1 (2), b= 1 845.2(12), c= 641.3(1) pm, β= 98.74(1)°, and Z= 2; R= 0.062 for 904 unique observed reflections. The four-membered ring with two trans exocyclic sulphurs possesses a crystallographic centre of symmetry.

Chemischer InformationsdienstVolume 13, Issue 30 Preparative Organic Chemistry ChemInform Abstract: PREPARATION AND REACTIONS OF S,N-BIS(HEPTAFLUOROISOPROPYL)SULFUR FLUORIDE IMIDE C. LENSCH, C. LENSCHSearch for more papers by this authorO. GLEMSER, O. GLEMSERSearch for more papers by this author C. LENSCH, C. LENSCHSearch for more papers by this authorO. GLEMSER, O. GLEMSERSearch for more papers by this author First published: July 27, 1982 https://doi.org/10.1002/chin.198230146AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume13, Issue30July 27, 1982 RelatedInformation

AbstractDurch Reaktionen von NSF3 mit den entsprechenden Perfluoralkylschwefeltrifluoriden in Gegenwart von HF werden die N‐Pentafluorsulfanyl‐schwefelmonofluoridimide (III) dargestellt.

S-Perfluoroalkyl-N-pentafluorosulphanyl sulphurmonofluoride imides (Rt - CF3 (1a) , t-C3F7 (1b)) are prepared by the reaction of NSF3 with appropriate sulphurtrifluoride derivatives. The fluorine bonded to sulphur(IV) in 1a and 1b is substituted by PCl5 to give sulphurmonochloride imides (Rt = CF3 (2a), i-C3F7 (2b)). The chlorine in 2a and 2b can be exchanged by reaction with suitable silver(I) and mercury(II) salts.

Abstract The Compound [S(AUPPh3)2] · CH2Cl2 was prepared from Ph3PAuCl and H2S in CH2Cl2 and characterised by X-ray structure determination [P21/c, a = 1851.6(4), b = 2225.1(6), c = 880.3(2) pm, β = 96.32(1)°, Z = 4, R = 0.053]. A constrained refinement of the light atom positions was necessary because of pseudosymmetry. Ph3PAuPF6 reacts with Se(Sn)(CH3)3)2 to give [Se(AuPPh3)3]+PF6- which was also characterised by X-ray methods [P1̄, a = 1539.5(6), b = 1800.5(7), c = 2289.5(9) pm, α = 89.35(3), β = 72.44(3), γ = 69.75(3)°, Z = 4, R = 0.061]. There are two formula units in the asymmetric unit. Both structures show short Au···Au contacts (ca. 300-340 pm).

S,N-Bis(heptafluoroisopropyl)sulphurfluorideimide (1) is prepared by the reaction of i-C3F7SF3 with (CF3)2CNH in the presence of CsF. The reaction with AlCl3 leads to two elimination products 4 and 5. With XeF2 the sulphur(II) atom in 4 and 5 is oxidized. In 1 the sulphur-bonded fluorine can be substituted by -OCH3 to give i-C3F7NS(i-C3F7)OCH3 (7).