Review
Noncoordinating Anions—Fact or Fiction? A Survey of Likely Candidates
Ingo Krossing Priv.-Doz. Dr.,
Ines Raabe Dipl.-Chem.,
Ingo Krossing Priv.-Doz. Dr.
University of Karlsruhe, Engesserstrasse Geb. 30.45, 76128 Karlsruhe, Germany, Fax: (+49) 721-608-4854
Search for more papers by this authorInes Raabe Dipl.-Chem.
University of Karlsruhe, Engesserstrasse Geb. 30.45, 76128 Karlsruhe, Germany, Fax: (+49) 721-608-4854
Search for more papers by this authorIngo Krossing Priv.-Doz. Dr.,
Ines Raabe Dipl.-Chem.,
Ingo Krossing Priv.-Doz. Dr.
University of Karlsruhe, Engesserstrasse Geb. 30.45, 76128 Karlsruhe, Germany, Fax: (+49) 721-608-4854
Search for more papers by this authorInes Raabe Dipl.-Chem.
University of Karlsruhe, Engesserstrasse Geb. 30.45, 76128 Karlsruhe, Germany, Fax: (+49) 721-608-4854
Search for more papers by this authorGraphical Abstract
Weak but not meek: Weakly coordinating anions (WCAs) are capable of the stabilization of sensitive cations in condensed phases (see structure of [Ag(η2-C2H4)3]+[Al{OC(CF3)3}4]−). In this Review the latest developments with respect to fundemental and applied chemistry are summarized and the criteria for choosing the most suitable WCA for a particular system are explored.
Abstract
Is there anything resembling a truly noncoordinating anion? Would it not be great to be able to prepare any crazy, beautiful, or simply useful cationic species that one has in mind, or has detected by mass spectroscopy? In condensed phases the target cation has to be partnered with a suitable counteranion. This is the moment when difficulties arise and many wonderful ideas end in the sink owing to coordination or decomposition of the anion. However, maybe these counteranion problems can be overcome by one of the new weakly coordinating anions (WCAs). Herein is an overview on the available candidates in the quest for the least coordinating anion and a summary of new applications, available starting materials, and general strategies to introduce a WCA into a system. Some of the unusual properties of WCA salts such as high solubility in low dielectric media, pseudo gas-phase conditions in condensed phases, and the stabilization of weakly bound and low-charged complexes are rationalized on thermodynamic grounds. Limits of the WCAs, that is, anion coordination and decomposition, are shown and a quantum chemical analysis of all types of WCAs is presented which allows the choice of a particular WCA to be based on quantative data from a wide range of different anions.
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- 181To evaluate the FIA of SbnF2n (n=2, 3, 4) giving the fluoride-bridged ions [SbnF5n+1]− the FIA was calculated by two separate calculations: 1) The FIA of the doubly fluoride-bridged Al2F6 (D2h) for the formation of the singly fluoride-bridged [Al2F7]− ion was calculated based on the average of G2 and CBS-Q calculations as 501 kJ mol−1. This step is non-isodesmic but the G2 and CBS-Q levels are reported to reproduce experimental values with a uncertainty of less than 8 kJ mol−1 lending credibility to these values. 2) The FIA of SbnF2n (n=2, 3, 4) was then calculated by adding the reaction enthalpy of the isodesmic reaction [Al2F7]− + SbnF2n→[SbnF2n+1]− + Al2F6 to the FIA of Al2F6 (501 kJ mol−1; see Equations 37 a–d)
for an example for [Sb2F11]−). Similarly the FIA of [(RO)3Al-F-Al(OR)3]− and [F4C6{1,2-B(C6F5)2}2F]− was assessed in isodesmic reactions of [Al2F7]− and the Lewis acid 2 Al(OR)3 and F4C6{1,2-(B(C6F5)2}2 giving 2 AlF3 and the fluoride-bridged ion. From this reaction enthalpy and the FIA of 2 AlF3—determined as the average of G2 and CBS-Q calculations (−706 kJ mol−1)—the FIA of 2 Al(OR)3 and F4C6{1,2-(B(C6F5)2}2 was calculated (see Equation 38 a–d)
for an example for [(RO)3Al-F-Al(OR)3]−).
- 182The LA was partitioned in two separate reactions: the first was an isodesmic reaction with which even very large systems could be calculated reliably at the BP86/SVP level [Eq. (39 a)
]. The second reaction contains much smaller species, however, is non-isodesmic. Therefore the computationally much more time consuming but also more reliable MP2/TZVPP level was selected to assess the second part (It is currently impossible to run also the first reaction at the MP2 level). The LA was than obtained by a simple addition of both equations [Eq. (39 c)].
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