Dynamic 13C NMR studies of ligand exchange in linear (d10) silver(I) and gold(I) and square-planar (d8) rhodium(I) homoleptic metal carbonyl cations in superacidic media.
The dynamic CO exchange of the monovalent metal carbonyl cations [Ag(13CO)]+, [Au(13CO)2]+-Au(13CO) SO3F and [Rh(12CO)4-x(13CO)x]+ (x < or = 1) in superacidic solutions was studied by variable-temperature 13C NMR methods. The exchange rates are strongly dependent on the acidity of the solvent, the concentration of metal carbonyl cations and temperature. Whereas a suitable exchange rate of the Ag(I) system is only accessible in magic acid (HSO3F-SbF5), the more stable Au(I) and Rh(I) systems were studied in the less acidic fluorosulfuric acid. Selected solutions of Ag(I), Rh(I) and Au(I) yielded activation barriers deltaG* of 42.7, 43.5, and 56.2 kJ mol(-1) respectively.
von Ahsen
B
B
Bergische Universität Wuppertal, Fachbereich C--Anorganische Chemie, Gaussstrasse 20, D-42119 Wuppertal, Germany.
Bach
C
C
Balzer
G
G
Bley
B
B
Bodenbinder
M
M
Hägele
G
G
Willner
H
H
Aubke
F
F
D000143:Acids / Q000737:chemistry*; D002244:Carbon / Q000032:analysis / Q000737:chemistry*; D002247:Carbon Isotopes; D002412:Cations; D006046:Gold / Q000032:analysis / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008670:Metals / Q000032:analysis / Q000737:chemistry; D012238:Rhodium / Q000032:analysis / Q000737:chemistry*; D012834:Silver / Q000032:analysis / Q000737:chemistry*; D012996:Solutions
D000143:Acids; D002247:Carbon Isotopes; D002412:Cations; D008024:Ligands; D008670:Metals; D012996:Solutions; D012834:Silver; D002244:Carbon; D006046:Gold; D012238:Rhodium