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Dynamic C-13 NMR studies of ligand exchange in linear (d(10)) silver(I) and gold(I) and square-planar (d(8)) rhodium(I) homoleptic metal carbonyl cations in superacidic media

TitleDynamic C-13 NMR studies of ligand exchange in linear (d(10)) silver(I) and gold(I) and square-planar (d(8)) rhodium(I) homoleptic metal carbonyl cations in superacidic media
Publication TypeJournal Article
Year of Publication2005
Authorsvon Ahsen, B, Bach, C, Balzer, G, Bley, B, Bodenbinder, M, Hagele, G, Willner, H, Aubke, F
JournalMagnetic Resonance in Chemistry
Volume43
Pagination520-527
Date PublishedJul
Type of ArticleArticle
ISBN Number0749-1581
KeywordsC-13 NMR, CO exchange, CRYSTAL, dynamic NMR, fluorosulfuric acid, GOLD, HINDERED INTERNAL ROTATION, HSO3F-SBF5, magic acid, metal carbonyl cations, NMR, NUCLEAR-MAGNETIC-RESONANCE, rhodium, silver, UNDECAFLUORODIANTIMONATE(V), VIBRATIONAL-SPECTRA
Abstract

The dynamic CO exchange of the monovalent metal carbonyl cations [Ag((CO)-C-13)](+), [Au((CO)-C-13)(2)](+)-Au((CO)-C-13) SO3F and [Rh((CO)-C-12)(4-x)((CO)-C-13)(x)](+) (x <= 1) in superacidic solutions was studied by variable-temperature C-13 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 Delta G* of 42.7, 43.5, and 56.2 kJ mol(-1) respectively. Copyright (c) 2005 John Wiley & Sons, Ltd.

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