The new homoleptic carbonyl cations [ R ~( C 0 ) ~1 2 + and [os(co)6]2+ are obtained as [Sb2FI11-salts by the reductive carbonylation of M(S03F)3 (M = Ru, Os), under very mild conditions (60-90 "C, 1 atm CO), in liquid SbF5 in a simple, one-step procedure, and are characterized by FT Raman, FTlR and 13C MAS NMR spectroscopy.

The original synthetic routes to the new noble metal carbonyl cations [Au(CO)2]+ and [M(CO)4]2+, M = Pd or Pt, as [Sb2F11]−salts are multi-step procedures that involve corrosive reagents and require commercially unavailable starting materials. We report here two general simplifications: (i) the sole use of liquid antimony(V) fluoride as reaction medium in a single-step carbonylation process, and (ii) the use of the commercially available chlorides AuCl3 and MCl2, M = Pd or Pt, as starting materials, in addition to the binary fluorosulfates Au(SO3F)3, Pd[Pd(SO3F)6], and Pt(SO3F)4. The simplified routes developed here for [Au(CO)2][Sb2F11] and [M(CO)4][Sb2F11]2, M = Pd or Pt, should make these new reagents more easily available for wider use in synthesis. In addition, these routes are found suitable for the generation of new carbonyl cations of electron-rich metals. Key words: metal carbonyl cations of Au(I), Pd(I), Pd(II), and Pt(II); solvolysis reactions in liquid SbF5, reductive carbonylation in liquid SbF5; carbonylations in strong acidic media.

Solvolysis Reactions in Liquid Antimony(V) Fluoride. A Convenient and Versatile Synthetic Method -(¿ 60 refs.) -(WANG, C.; HWANG, G.; SIU, S. C.; AUBKE, F.; BLEY, B.; BODENBINDER, M.; BACH, C.; WILLNER, H.; Eur. J. Solid State Inorg. Chem. 33 (1996) 9, 917-930; Dep. Chem., Univ. British Columbia, Vancouver, B. C. V6T 1Z1, Can.; EN)