In‐Between Complex and Cluster: A 14‐Vertex Cage in [Ag2Se12]2+

Köchner, Tobias; Trapp, Nils; Engesser, Tobias A.; Lehner, Anna J.; Röhr, Caroline; Riedel, Sebastian; Knapp, Carsten; Scherer, Harald; Krossing, Ingo

doi:10.1002/anie.201104666

Cited by 32 publications

(20 citation statements)

References 29 publications

(28 reference statements)

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“…For 4 a and 4 c , including the WCA [TEF], there are severe problems concerning the single‐crystal X‐ray diffraction analysis . However, the molecular structures of the respective cations [ 2 a ] + and [ 2 b ] + could unambiguously be determined with the help of the WCA [FAl] in 4 b and 4 d . Single‐crystal X‐ray structure determination reveals that the cyclo ‐E 6 complexes 2 a – 3 retain the triple‐decker geometry upon one‐electron oxidation .…”

Section: Methodsmentioning

confidence: 99%

Oxidation Chemistry of Inorganic Benzene Complexes

Fleischmann

Dielmann

Baláȥs

et al. 2016

Chemistry A European J

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The oxidation of the 28 VE cyclo-E triple-decker complexes [(Cp Mo) (μ,η :η -E )] (E=P, Cp =Cp(2 a), Cp*(2 b), Cp (2 c)=C (CH Ph) ; E=As, Cp =Cp*(3)) by Cu or Ag leads to cationic 27 VE complexes that retain their general triple-decker geometry in the solid state. The obtained products have been characterized by cyclic voltammetry (CV), EPR, Evans NMR, multinuclear NMR spectroscopy, MS, and structural analysis by single-crystal X-ray diffraction. The cyclo-E middle decks of the oxidized complexes are distorted to a quinoid (2 a) or bisallylic (2 b, 2 c, 3) geometry. DFT calculations of 2 a, 2 b, and 3 persistently result in the bisallylic distortion as the minimum geometry and show that the oxidation leads to a depopulation of the σ-system of the cyclo-E ligands in 2 a-3. Among the starting complexes, 2 c is reported for the first time including its preparation and full characterization.

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Section: Methodsmentioning

confidence: 99%

Oxidation Chemistry of Inorganic Benzene Complexes

Fleischmann

Dielmann

Baláȥs

et al. 2016

Chemistry A European J

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“…Decomposition via abstraction of an –OR F ligand [pathway (i)] can be reduced by either increasing the steric shielding of the oxygen atoms ( kinetic stability) or by increasing the Lewis acidity of the parent Lewis acid of the WCA [in this case Al(OR F ) 3 ] increasing its thermodynamic stability. The incorporation of four –OR F ligands to form [Al(OR F ) 4 ] – is already approaching the upper limit of steric bulk for the formation of an homoleptic aluminate WCA . Therefore, we turned our attention to the question of increasing thermodynamic stability and the formation of a novel WCA based on a stronger parent Lewis acid than Al(OR F ) 3 .…”

Section: Introductionmentioning

confidence: 99%

Towards Weakly Coordinating Anions with the Extremely Electron Withdrawing Perfluoropyridinoxy Ligand –OC₅F₄N

et al. 2018

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The extreme electron withdrawing properties of the perfluoropyridinoxy ligand –OC5F4N were used for the preparation of new (weakly) coordinating borate and aluminate anions of the type [E(OC5F4N)4]– (E = B or Al). These new anions are based on the potent parent Lewis acids E(OC5F4N)3, which possess exceptionally high calculated fluoride ion affinities (FIAs) of 500 and 587 kJ mol–1 for E = B and Al respectively. For aluminum, this extreme Lewis acidity dominates the chemistry and from mixtures of the neutral polymeric Lewis acid [Al(OC5F4N)3]n, the five‐ and six‐coordinate complexes Al(OC5F4N)3(OEt2)2 (1) and [Al(OC5F4N)2(µ‐OC5F4N) (NCMe)2]2 (2) were crystallized upon addition of ether or MeCN. The aluminate salts M[Al(OC5F4N)4] (M = Li or K) were prepared from the reaction between the alcohol 4‐HO–C5F4N and either LiAlH4 or K[AlEt4] respectively. The aluminate anion [Al(OC5F4N)4]– remains Lewis acidic coordinating small donor molecules forming [Al(OC5F4N)4(L)]– (L = THF or NMe3) and even supports formation and structural characterisation of the aluminum dianion containing salt [Na(OEt2)2][Na][Al(OC5F4N)5] (8). The from NaBH4 and 4‐HO–C5F4N accessible borate salt Na[B(OC5F4N)4] shows increased kinetic stability in comparison to the aluminum analogue.

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“…The dark teal crystals of 3 a were not suitable for an X-ray structure analysis. [24] By exchanging the anion [TEF] for another WCA [FAl{OC 6 F 10 (C 6 F 5 )} 3 ] − ([FAl]),[25] we were able to determine the crystal structure of the oxidized P 6 complex 3 b (Figure 2). …”

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confidence: 99%

Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)₂(μ,η⁶:η⁶‐P₆)] Towards the “Naked” Cations Cu⁺, Ag⁺, and Tl⁺

et al. 2015

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Although the cyclo-P6 complex [(Cp*Mo)2(μ,η6:η6-P6)] (1) was reported 30 years ago, little is known about its chemistry. Herein, we report a high-yielding synthesis of 1, the complex 2, which contains an unprecedented cyclo-P10 ligand, and the reactivity of 1 towards the “naked” cations Cu+, Ag+, and Tl+. Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo-P6 middle deck, the [M(1)2]+ complexes are described which show distorted square-planar (M=Cu(4 a), Ag(4 b)) or distorted tetrahedral coordinated (M=Cu(5)) M+ cations. The choice of solvent enabled control over the reaction outcome for Cu+, as proved by powder XRD and supported by DFT calculations. The reaction with Tl+ affords a layered two-dimensional coordination network in the solid state.

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In‐Between Complex and Cluster: A 14‐Vertex Cage in [Ag₂Se₁₂]²⁺

Cited by 32 publications

References 29 publications

Oxidation Chemistry of Inorganic Benzene Complexes

Oxidation Chemistry of Inorganic Benzene Complexes

Towards Weakly Coordinating Anions with the Extremely Electron Withdrawing Perfluoropyridinoxy Ligand –OC₅F₄N

Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)₂(μ,η⁶:η⁶‐P₆)] Towards the “Naked” Cations Cu⁺, Ag⁺, and Tl⁺

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In‐Between Complex and Cluster: A 14‐Vertex Cage in [Ag2Se12]2+

Cited by 32 publications

References 29 publications

Oxidation Chemistry of Inorganic Benzene Complexes

Oxidation Chemistry of Inorganic Benzene Complexes

Towards Weakly Coordinating Anions with the Extremely Electron Withdrawing Perfluoropyridinoxy Ligand –OC5F4N

Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)2(μ,η6:η6‐P6)] Towards the “Naked” Cations Cu+, Ag+, and Tl+

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In‐Between Complex and Cluster: A 14‐Vertex Cage in [Ag₂Se₁₂]²⁺

Towards Weakly Coordinating Anions with the Extremely Electron Withdrawing Perfluoropyridinoxy Ligand –OC₅F₄N

Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)₂(μ,η⁶:η⁶‐P₆)] Towards the “Naked” Cations Cu⁺, Ag⁺, and Tl⁺