Reactions of diaminophosphenium and 1,3,2-diazaphospholenium triflates with silver salts

✍ Scribed by Gudat, Dietrich ;Holderberg, Andreas W. ;Kotila, Sirpa ;Nieger, Martin

• Publisher: Wiley (John Wiley & Sons)
• Year: 1996
• Tongue: English
• Weight: 579 KB
• Volume: 129
• Category: Article
• ISSN: 0009-2940
• DOI: 10.1002/cber.19961290416

✦ Synopsis

Phosphenium cations / Silver complexes / 31P,109Ag NMR shift correlation Reaction of bis(diisopropy1amino)phosphenium triflate (l[CF3S03]) with silver salts AgY [Y-= CF3C0, (Za), CF:{-SO, (2b), CH3C0y (2c)l affords neutral complexes [[(iPr,N),(Y)P) Ag(OS02CF3)] (3a -c). While 3a, c are stable up to ambient temperature, 3b is only stable at low temperature and in equilibrium with the cation 1. The constitution of 3a-c was derived from multinuclear (IH, I3C, "P, ""Ag) NMR spectra. Compound 3a was further studied by X-ray single-crystal diffractommetry which showed the presence of dimeric units with p2-bridging triflate ligands and three-coor-dinate silver atoms with a planar T-shaped coordination geome try. Reaction of 4 -chlorol ,3-bis (2,6-dime thylphenyl) -1,3,2-diazaphospholenium triflate (4[CF3S03]) with 2a, c affords equilibrium mixtures whose 31P-and IogAg-NMR spectra suggested the presence of silver complexes 5a, c with constitutions similar to those of 3a, c besides unreacted cation 4. No reaction was observed between 4[CF,SO,] and 2b. A common mechanism accounting for the different outcome of the individual reactions will be discussed.