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The synthesis, vibrational spectra, and molecular structure of [Ir(CO)(6)][SbF6](3)center dot 4HF - The first structurally characterized salt with a tripositive, homoleptic metal carbonyl cation and the first example of a tetrahedral hydrogen-bonded (HF)(

TitleThe synthesis, vibrational spectra, and molecular structure of [Ir(CO)(6)][SbF6](3)center dot 4HF - The first structurally characterized salt with a tripositive, homoleptic metal carbonyl cation and the first example of a tetrahedral hydrogen-bonded (HF)(
Publication TypeJournal Article
Year of Publication2002
Authorsvon Ahsen, B, Berkei, M, Henkel, G, Willner, H, Aubke, F
JournalJournal of the American Chemical Society
Volume124
Pagination8371-8379
Date PublishedJul
Type of ArticleArticle
ISBN Number0002-7863
Keywords<IR(CO)(6)>(3+), CARBOCATIONS, CHEMISTRY, CRYSTAL-STRUCTURES, IR, MO, OS, RU, SUPERACID MEDIA, UNDECAFLUORODIANTIMONATE(V)
Abstract

{The reductive carbonylation of IrF6 in a dilute solution of SbF5 in anhydrous HF (1:6 by volume) produces surprisingly at 25 degreesC and 1.5 atm CO the complex salt [Ir(CO)(6)][SbF6](3).4HF, while [Ir(CO)(6)][Sb2F11](3) is obtained in liquid SbF5 under similar conditions. Vibrational spectra in the CO stretching range for both salts and [Ir(CO)(6)](3+)((solv)) are identical within error limits, and v(CO)(av) is with 2269 cm(-1) the highest average stretching frequency so far observed for octahedral metal carbonyl cations. A vibrational assignment supported by DFT calculations is presented, and the vibrational fundamentals are compared to those of [OS(CO)(6)](2+). The molecular structure of [Ir(CO)(6)][SbF6](3).4HF is determined by single-crystal X-ray diffraction. Crystal data for [Ir(CO)(6)][SbF6](3).4HF: rhombohedral, R3c (No. 161)

URL<Go to ISI>://000176843200032