Phosphorus-fluorine chemistry. XXVII. Aryloxy-substituted fluorophosphoranes

Abstract

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:

Trinuclear Half‐Sandwich RuII, RhIII and IrIII Polyester Organometallic Complexes: Synthesis and in vitro Evaluation as Antitumor Agents

“…The cationic complexes 5 – 7 and 11 – 13 display a septet signal in the 31 P{ 1 H} NMR spectra for the counterion, PF 6 – , in the range –144.25 to –144.21 ppm, which is in accordance with the literature value for other hexafluorousphosphate salts 26,27. These complexes display mass‐to‐charge ( m / z ) signals corresponding to [M – PF 6 ] + for the monomeric complexes or [M – 3PF 6 ] 3+ for the trimeric complexes, while the neutral complexes 8 – 10 and 14 – 16 display m / z peaks corresponding to [M – Cl] + for the monomeric or [M – 3Cl] 3+ for the trimeric complexes, respectively.…”

Oxo Ligand Reactivity in the [ReO2L4]+ Complex of 1-Methylimidazole. Preparation and Crystal Structures of Salts Containing the ReOL43+ Core and Apical CH3O-, BF3O2-, and (CH3O)2PO2- Groups

“…Initial acid-promoted displacement of F - from PF 6 - is likely followed by relatively fast alcoholysis processes known to occur with PF 5 , − generating various intermediate fluoro−oxo−alkoxo species and, finally, phosphate esters. The reaction does not reach the PO(OCH 3 ) 3 stage, probably because the third methoxy group is relative easy to displace .…”

Improving the accuracy of 31P NMR chemical shift calculations by use of scaling methods

“…For the tetracoordinate phosphorus compounds, NMR chemical shifts (referenced to external 85% H 3 PO 4 at 0.00 ppm, positive values downfield) were measured in CDCl 3 on a 400 MHz Bruker spectrometer for (iPrO) 2 P(O)H (4.54 ppm), Ph 4 P + Br − (23.17 ppm), and (iPrO) 2 P(O)Me (28.61 ppm) or were taken from the literature: PH 4 + BF 4 − (−105.3 ppm in CH 3 OH/CH 3 OD solution [ 109 – 110 ]), (PhO) 4 P + PF 6 − (−28.0 ppm in CH 3 CN solution [ 111 ]), O= P ( OCH 2 ) 3 P=O (−18.1 ppm in DMSO solution [ 112 ]), O=P ( OCH 2 ) 3 P =O (6.4 ppm in DMSO solution [ 112 ]), (MeO) 4 P + BF 4 − (1.9 ppm in CH 2 Cl 2 solution [ 113 ]), (MeO) 2 P(O)H (11.3 ppm, liquid sample [ 45 ]), Me 4 P + Br − (25.1 ppm in DMSO solution [ 114 ]), Ph 3 P=O (29.10 ppm in CDCl 3 solution [ 115 ]), (MeO) 2 P(O)Me (32.3 ppm, liquid sample [ 116 ]), Me 3 P=O (38.79 ppm in CDCl 3 solution [ 115 ]), EtOP(O)Me 2 (50.3 ppm, liquid sample [ 43 ]).…”