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
✍ Scribed by B. von Ahsen; C. Bach; G. Balzer; B. Bley; M. Bodenbinder; G. Hägele; H. Willner; F. Aubke
- Publisher
- John Wiley and Sons
- Year
- 2005
- Tongue
- English
- Weight
- 179 KB
- Volume
- 43
- Category
- Article
- ISSN
- 0749-1581
- DOI
- 10.1002/mrc.1587
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✦ Synopsis
The dynamic CO exchange of the monovalent metal carbonyl cations [Ag( 13 CO)] + , [Au( 13 CO) 2 ] + -Au( 13 CO) SO 3 F and [Rh( 12 CO) 4-x ( 13 CO) x ] + (x 1) in superacidic solutions was studied by variable-temperature 13 C 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 (HSO 3 F-SbF 5 ), 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 1G * of 42.7, 43.5, and 56.2 kJ mol -1 respectively.