Predominantly σ‐Bonded Metal Carbonyl Cations (σ‐Carbonyls): New Synthetic, Structural, and Bonding Concepts in Metal Carbonyl Chemistry
- 26 March 2003
- journal article
- concept
- Published by Wiley in Chemistry – A European Journal
- Vol. 9 (8) , 1668-1676
Abstract
Predominantly σ‐bonded metal carbonyl cations (σ‐carbonyls) are conveniently generated in the Lewis superacid SbF5 or the conjugate Brønsted–Lewis superacid HFSbF5, primarily by solvolytic or reductive carbonylations. Thermally stable salts are formed with the fluoroantimonate(V) ions [SbF6]− and [Sb2F11]−. The salts are characterised by analytical, structural, spectroscopic and computational methods. Most homoleptic carbonyl cations have very regular geometries, comensurate with their d‐electron configurations: linear (d10), square planar (d8) or octahedral(d6). The cations with metals in oxidation states of +2 or +3 are termed “superelectrophilic”. Extended molecular structures form by significant interionic CF contacts with electrophilic carbon as acceptor. To account for all experimental observations, a conceptually simple synergetic bonding model is proposed. An outlook at anticipated future developments based on very recent results is provided.Keywords
This publication has 44 references indexed in Scilit:
- On a quantitative scale for Lewis acidity and recent progress in polynitrogen chemistryJournal of Fluorine Chemistry, 2000
- Hexakis(carbonyl)iron(II) Undecafluorodiantimonate(V), [Fe(CO)6][Sb2F11]2, and -Hexafluoroantimonate(V), [Fe(CO)6][SbF6]2, Their Syntheses, and Spectroscopic and Structural Characterization by Single Crystal X-ray Diffraction and Normal Coordinate AnalysisJournal of the American Chemical Society, 1999
- Fluoroanions and cations in the HF–SbF5 superacid system. A 19F and 1H NMR studyNew Journal of Chemistry, 1999
- Syntheses and Vibrational and13C MAS-NMR Spectra of Bis(carbonyl)mercury(II) Undecafluorodiantimonate(V) ([Hg(CO)2][Sb2F11]2) and of Bis(carbonyl)dimercury(I) Undecafluorodiantimonate ([Hg2(CO)2][Sb2F11]2) and the Molecular Structure of [Hg(CO)2][Sb2F11]2Inorganic Chemistry, 1996
- Nonclassical Metal Carbonyls: [Ag(CO)]+ and [Ag(CO)2]+Journal of the American Chemical Society, 1994
- SuperelektrophileAngewandte Chemie, 1993
- Bis(carbonyl)gold(I) undecafluorodiantimonate(V), [Au(CO)2][Sb2F11]: synthesis, vibrational, and carbon-13 NMR study and the molecular structure of bis(acetonitrile)gold(I) hexafluoroantimonate(V), [Au(NCCH3)2][SbF6]Journal of the American Chemical Society, 1992
- Thermodynamic behavior of alkanes in superacid mediaChemical Reviews, 1982
- Fluorosulfuric acid and related superacid mediaAccounts of Chemical Research, 1968
- Hard and Soft Acids and BasesJournal of the American Chemical Society, 1963