Chemistry with weakly-coordinating fluorinated alkoxyaluminate anions: Gas phase cations in condensed phases?

Krossing, Ingo; Reisinger, Andreas

doi:10.1016/j.ccr.2005.10.023

Cited by 209 publications

(160 citation statements)

References 171 publications

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“…Therefore the stability of 5 is thermodynamic and the preparation of 5 and 6 may be considered as further proof for the validity of our concept of pseudo-gas-phase conditions in condensed phases. [76,77,91] We have shown that determination of reasonable C=C bond lengths of free and complexed H 2 C=CH 2 is very difficult due to libration and the anisotropy of the electron density. Therefore we devised a simple method based on Raman spectroscopy, from which the spectroscopic C=C distance of [MA C H T U N G T R E N N U N G (h 2 -C 2 H 4 )] moieties can be extracted [Eqs.…”

Section: Discussionmentioning

confidence: 99%

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Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)

Reisinger

Trapp

Knapp

et al. 2009

Chemistry A European J

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Compounds including the free or coordinated gas-phase cations [Ag(eta(2)-C(2)H(4))(n)](+) (n = 1-3) were stabilized with very weakly coordinating anions [A](-) (A = Al{OC(CH(3))(CF(3))(2)}(4), n = 1 (1); Al{OC(H)(CF(3))(2)}(4), n = 2 (3); Al{OC(CF(3))(3)}(4), n = 3 (5); {(F(3)C)(3)CO}(3)Al-F-Al{OC(CF(3))(3)}(3), n = 3 (6)). They were prepared by reaction of the respective silver(I) salts with stoichiometric amounts of ethene in CH(2)Cl(2) solution. As a reference we also prepared the isobutene complex [(Me(2)C=CH(2))Ag(Al{OC(CH(3))(CF(3))(2)}(4))] (2). The compounds were characterized by multinuclear solution-NMR, solid-state MAS-NMR, IR and Raman spectroscopy as well as by their single crystal X-ray structures. MAS-NMR spectroscopy shows that the [Ag(eta(2)-C(2)H(4))(3)](+) cation in its [Al{OC(CF(3))(3)}(4)](-) salt exhibits time-averaged D(3h)-symmetry and freely rotates around its principal z-axis in the solid state. All routine X-ray structures (2theta(max.) < 55 degrees) converged within the 3sigma limit at C=C double bond lengths that were shorter or similar to that of free ethene. In contrast, the respective Raman active C=C stretching modes indicated red-shifts of 38 to 45 cm(-1), suggesting a slight C=C bond elongation. This mismatch is owed to residual librational motion at 100 K, the temperature of the data collection, as well as the lack of high angular data owing to the anisotropic electron distribution in the ethene molecule. Therefore, a method for the extraction of the C=C distance in [M(C(2)H(4))] complexes from experimental Raman data was developed and meaningful C=C distances were obtained. These spectroscopic C=C distances compare well to newly collected X-ray data obtained at high resolution (2theta(max.) = 100 degrees) and low temperature (100 K). To complement the experimental data as well as to obtain further insight into bond formation, the complexes with up to three ligands were studied theoretically. The calculations were performed with DFT (BP86/TZVPP, PBE0/TZVPP), MP2/TZVPP and partly CCSD(T)/AUG-cc-pVTZ methods. In most cases several isomers were considered. Additionally, [M(C(2)H(4))(3)] (M = Cu(+), Ag(+), Au(+), Ni(0), Pd(0), Pt(0), Na(+)) were investigated with AIM theory to substantiate the preference for a planar conformation and to estimate the importance of sigma donation and pi back donation. Comparing the group 10 and 11 analogues, we find that the lack of pi back bonding in the group 11 cations is almost compensated by increased sigma donation.

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Section: Discussionmentioning

confidence: 99%

“…[76,77] To investigate this point in more detail, two explicit cases with A = BF 4 and Al{OCA C H T U N G T R E N N U N G (CF 3 ) 3 } 4 were considered. The calculated Gibbs lattice potential energies (from volume-based Table 7.…”

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confidence: 99%

Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)

Reisinger

Trapp

Knapp

et al. 2009

Chemistry A European J

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“…This also holds for a series of silver and copper(I) complexes with very weakly basic ligands, for example, P 4 , [29,30] P 4 S 3 , [31,32] S 8 , [33] P 3 N 3 Cl 6 , [34] or C 2 H 4 . [35,36] Since the starting materials to prepare compounds of the fluorinated aluminates are commercially available (best at P&M Invest Russia; http:// www.fluorine.ru) and the synthesis of the lithium aluminate salts [37][38][39] is a simple high yield procedure that we have performed in scales up to 250 g per batch, [40] it only appeared logical to extend the available substance classes to [NR 4 ] + salts. During the preparation of this manuscript, an independent communication of the electrochemical windows of related compounds appeared.…”

Section: Introductionmentioning

confidence: 99%

Tetraalkylammonium Salts of Weakly Coordinating Aluminates: Ionic Liquids, Materials for Electrochemical Applications and Useful Compounds for Anion Investigation

Raabe

Wagner

Guttsche

et al. 2009

Chemistry A European J

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In this study, we investigated the tetraalkylammonium salts of the weakly coordinating fluorinated alkoxyaluminates [pftb](-) ([Al(O(C(CF(3))(3))(4)](-)), [hfip](-) ([Al(OC(H)(CF(3))(2))(4)](-)) and [hftb](-) ([Al(OC(CH(3))(CF(3))(2))(4)](-)) in order to obtain information on their undisturbed spectral and structural properties, as well as to study their electrochemical behavior (i.e., conductivities in non-polar solvents and electrochemical windows). Several of the compounds qualify as ionic liquids with melting points as low as 42 degrees C for [NBu(4)](+)[hfip](-). Simple and almost quantitative metathesis reactions yielding these materials in high purity were developed. These [NR(4)](+) salts serve as model compounds for undisturbed anions and their vibrational spectra--together with simulated spectra based on quantum chemical DFT calculations--were used for the clear assignment of the anion bands. Besides, the ion volumes of the anions (V(ion)([pftb](-)) = 0.736 nm(3), V(ion)([hftb](-)) = 0.658 nm(3), V(ion)([hfip](-)) = 0.577 nm(3)) and their decomposition pathways in the mass spectrometric measurements have been established. The salts are highly soluble in non-polar solvents (up to 1.09 mol L(-1) are possible for [NBu(4)](+)[hftb](-) in CH(2)Cl(2) and 0.41 mol L(-1) for [NBu(4)](+)[hfip](-) in CHCl(3)) and show higher molar conductivities if compared to [NBu(4)](+)[PF(6)](-). The electrochemical windows of CH(2)Cl(2), CH(3)CN and 1,2-F(2)C(6)H(4) using the [NBu(4)](+) aluminate electrolytes are up to +0.5 V/-0.7 V larger than those using the standard [NBu(4)](+)[PF(6)](-).

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“…Krossing À of 4 were disordered, numerous restraints (SADI) had to be used to order the atoms in appropriate positions, [22] which lead to somewhat elevated wR 2 values. For 5, a twinning refinement using the merohedral twin law (0 À1 0; À1 0 0; 0 0 À1) was applied.…”

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Unusual Coordination Behavior of P_n‐Ligand Complexes with Tl⁺

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Chemistry with weakly-coordinating fluorinated alkoxyaluminate anions: Gas phase cations in condensed phases?

Cited by 209 publications

References 171 publications

Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)

Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)

Tetraalkylammonium Salts of Weakly Coordinating Aluminates: Ionic Liquids, Materials for Electrochemical Applications and Useful Compounds for Anion Investigation

Unusual Coordination Behavior of P_n‐Ligand Complexes with Tl⁺

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Chemistry with weakly-coordinating fluorinated alkoxyaluminate anions: Gas phase cations in condensed phases?

Cited by 209 publications

References 171 publications

Silver–Ethene Complexes [Ag(η2‐C2H4)n][Al(ORF)4] with n=1, 2, 3 (RF=Fluorine‐Substituted Group)

Silver–Ethene Complexes [Ag(η2‐C2H4)n][Al(ORF)4] with n=1, 2, 3 (RF=Fluorine‐Substituted Group)

Tetraalkylammonium Salts of Weakly Coordinating Aluminates: Ionic Liquids, Materials for Electrochemical Applications and Useful Compounds for Anion Investigation

Unusual Coordination Behavior of Pn‐Ligand Complexes with Tl+

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Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)

Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)

Unusual Coordination Behavior of P_n‐Ligand Complexes with Tl⁺