No abstract

The IR and Raman spectra of disulfur dinitride, S(2)N(2), are reported not only for the solid condensate but also for the molecules isolated in solid noble gas, N(2), or CH(4) matrices at low temperatures. The results imply that the isolated S(2)N(2) molecule has much the same geometry as in the crystalline solid with a virtually square-planar structure conforming to D(2h) symmetry, a conclusion confirmed by isotopic enrichment in (15)N and by the results of earlier as well as fresh quantum chemical calculations. These calculations also support the results of normal coordinate analysis of the experimental data in giving potential constants suggestive of a relatively rigid S(2)N(2) molecule consistent with its description as a 2π-electron aromatic, while appearing to maintain a formal S-N bond order close to 1.

Alkylthio-and arylthio-fluorophosphoranes of the types RISPFp, R1S(R2)PF3, and R1S(R2)2PF2, (R1 = Me, Et, or Ph; R2 = Me or Ph) are prepared in good yields by the cleavage of sulphur-silicon bonds in trimethylsilylsulphides by fluorophosphoranes. The structures of the new compounds are deduced from l 9 F and 31P n.m.r. data.THE structures of fluorophosphoranes which contain hetero-atoms are of considerable interest,2 and since few compounds in this class were known, apart from those containing nitrogen as a hetero-atom, we were interested in preparing a series of mercapto-substituted fluorophosphoranes. These compounds were of particular interest since we expected that they would have greater thermal stability than their alkoxy-analogues which have a great tendency to decompose to (tetra-co-ordinate) phosphoryl species.2 Aminofluorophosphoranes of the general formula R,1NPR2,F4-, (R1 = Me, Et, or Ph; R2 = Me, Et, or Ph;?$ = 0, 1, or 2),3 are readily synthesised by the cleavage of the silicon-nitrogen bonds of aminosilanes by fluoro-

The preparation of 1.3.2-dithiaphospholans and their 2-0x0-and 2-thioxo-derivatives is described. l H and slP N.m.r. data are reported and discussed. The l H n.m.r. spectra of four dithiaphospholans have been fully analysed on the basis of an [AB],X system, giving values for the l H chemical shifts, the (H,H) coupling constants of the CH,*CH, group and the (H,P) coupling constants involving that group.

ent in the solution, (d) CFsP(S)C122 (0.0490 g, 0.24 mmol) yielded no fluorocarbon-containing volatiles, but the solution contained the CFsPSCh2-ion. (e) (CF3)2PS2H2•3 (0.0791 g, 0.34 mmol) yielded CF3H (0.0237 g, 0.34 mmol) and the CF3PS2Q2ĩ on in solution. The solution gave a negative test for the sulfide ion. (f) (CF3)2P(0)SCH39 (0.0320 g, 0.14 mmol) yielded CF8H (0.0113 g, 0.16 mmol) and both sulfide and CF3P032~ions remained in the hydrolysate, (g) (CF3)2P(S)OCH39 (0.0870 g, 0.38 mmol) yielded CF3H (0.0290 g, 0.41 mmol) and the aqueous solution contained CF3PS022-but no sulfide ion. (h) (CF3)2P-(S)SCH32 (0.0847 g, 0.34 mmol) produced CFSH (0.0278 g, 0.40 mmol) and the hydrolysate contained CF3PSO22-and sulfide ions, (i) Slightly impure (CF3)3P=S (0.1189 g, 0.44 mmol) yielded CF3H (0.0588 g, 0.84 mmol) and an aqueous solution which contained the CF3PSO22-ion.(2) Diphosphorus Compounds.-(a) (CF3)2P(S)SP(CF3)21 (0.0533 g, 0.13 mmol) gave CF3H (0.0279 g, 0.39 mmol) and CF3PS202-remained in solution, (b) (CF3)2P(S)SSP(S)(CF3)2l (0.0558 g, 0.12 mmol) produced CF3H (0.0175 g, 0.25 mmol). The aqueous solution contained the CF3PS2O2-and CF3PSO22ions in the ratio 3:1. A little elemental sulfur was also obtained, but no sulfide ion was present in the solution, (c) (CF3)2P-(S)OP(S)(CF3)29 (0.0636 g, 0.15 mmol) yielded CF3H (0.0207 g, 0.30 mmol) and CF3PSO22-remained in solution. The absence of sulfide ion in the solution was demonstrated.Reactions with Hydrogen Peroxide.-Reactions were carried out by condensing the reactants onto 1.0 ml of 5% H2O2 solution and allowing the reaction to continue at room temperature for 4 days, (a) (CF3)2PS2H2'3 (0.30 mmol) began to react as soon as the tube reached room temperature with appearance of elemental sulfur. The solution contained the (CF3)2P02"" ion and another unidentified CF3P-containing species, (b) (CF3)2-P(S)C12'3 (0.30 mmol) reacted as above to yield the same species in solution and elemental sulfur.Preparation of Tetraphenylarsonium Salts.(1) (C6H3)4As+-CF3PS02H~.-Trifluoromethylthiophosphoryl dichloride2 (0.1257 g, 0.62 mmol) was hydrolyzed with 5.0 ml of 10% NaOH solution for 6 days. The tube was then opened and tetraphenylarsonium chloride (1.0 g, 2.4 mmol) dissolved in the minimum amount of water was added. The salt was precipitated by acidifying with concentrated hydrochloric acid dropwise using phenolphthalein indicator. The white solid was filtered off and dried under vacuum at room temperature. The yield of salt was 0.281 g (0.512 mmol). Anal. Caled for C23H2iAsPF3S02: