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- ItemPseudohalogen Chemistry in Ionic Liquids with Non-innocent Cations and Anions(Weinheim : Wiley-VCH-Verl., 2020) Arlt, Sören; Bläsing, Kevin; Harloff, Jörg; Laatz, Karoline Charlotte; Michalik, Dirk; Nier, Simon; Schulz, Axel; Stoer, Philip; Stoffers, Alrik; Villinger, AlexanderWithin the second funding period of the SPP 1708 “Material Synthesis near Room Temperature”,which started in 2017, we were able to synthesize novel anionic species utilizing Ionic Liquids (ILs) both, as reaction media and reactant. ILs, bearing the decomposable and non-innocent methyl carbonate anion [CO3Me]−, served as starting material and enabled facile access to pseudohalide salts by reaction with Me3Si−X (X=CN, N3, OCN, SCN). Starting with the synthesized Room temperature Ionic Liquid (RT-IL) [nBu3MeN][B(OMe)3(CN)], we were able to crystallize the double salt [nBu3MeN]2[B(OMe)3(CN)](CN). Furthermore, we studied the reaction of [WCC]SCN and [WCC]CN (WCC=weakly coordinating cation) with their corresponding protic acids HX (X=SCN, CN), which resulted in formation of [H(NCS)2]− and the temperature labile solvate anions [CN(HCN)n]− (n=2, 3). In addition, the highly labile anionic HCN solvates were obtained from [PPN]X ([PPN]=μ-nitridobis(triphenylphosphonium), X=N3, OCN, SCN and OCP) and HCN. Crystals of [PPN][X(HCN)3] (X=N3, OCN) and [PPN][SCN(HCN)2] were obtained when the crystallization was carried out at low temperatures. Interestingly, reaction of [PPN]OCP with HCN was noticed, which led to the formation of [P(CN)2]−, crystallizing as HCN disolvate [PPN][P(CN⋅HCN)2]. Furthermore, we were able to isolate the novel cyanido(halido) silicate dianions of the type [SiCl0.78(CN)5.22]2− and [SiF(CN)5]2− and the hexa-substituted [Si(CN)6]2− by temperature controlled halide/cyanide exchange reactions. By facile neutralization reactions with the non-innocent cation of [Et3HN]2[Si(CN)6] with MOH (M=Li, K), Li2[Si(CN)6] ⋅ 2 H2O and K2[Si(CN)6] were obtained, which form three dimensional coordination polymers. From salt metathesis processes of M2[Si(CN)6] with different imidazolium bromides, we were able to isolate new imidazolium salts and the ionic liquid [BMIm]2[Si(CN)6]. When reacting [Mes(nBu)Im]2[Si(CN)6] with an excess of the strong Lewis acid B(C6F5)3, the voluminous adduct anion {Si[CN⋅B(C6F5)3]6}2− was obtained. © 2020 The Authors. Published by Wiley-VCH GmbH
- ItemCorrection: Increasing steric demand through flexible bulk – primary phosphanes with 2,6-bis(benzhydryl)phenyl backbones(London : Soc., 2019) Bresien, Jonas; Goicoechea, Jose M.; Hinz, Alexander; Scharnhölz, Moritz T.; Schulz, Axel; Suhrbier, Tim; Villinger, AlexanderCorrection for 'Increasing steric demand through flexible bulk-primary phosphanes with 2,6-bis(benzhydryl)phenyl backbones' by Jonas Bresien et al., Dalton Trans., 2019, 48, 3786-3794. © 2019 The Royal Society of Chemistry.
- ItemA Systematic Survey of the Reactivity of Chlorinated N2P2, NP3 and P4 Ring Systems(Weinheim : Wiley-VCH, 2019) Bresien, Jonas; Eickhoff, Liesa; Schulz, Axel; Suhrbier, Tim; Villinger, AlexanderThe reactivity of the four-membered NP3 ring system [RN(μ-PCl)2PR] (R=Mes*=2,4,6-tri-tert-butylphenyl) towards Lewis acids, Lewis bases, and reducing agents was investigated. Comparisons with the literature-known, analogous cyclic compounds [ClP(μ-NR)]2 (R=Ter=2,6-dimesitylphenyl) and [ClP(μ-PR)]2 (R=Mes*) are drawn, to obtain a better systematic understanding of the reactivity of cyclic NP species. Apart from experimental results, DFT computations are discussed to further the insight into bonding and electronic structure of these compounds. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemFacile Synthesis of a Stable Side-on Phosphinyne Complex by Redox Driven Intramolecular Cyclisation(Weinheim : Wiley-VCH, 2020) Lange, Helge; Schröder, Henning; Oberem, Elisabeth; Villinger, Alexander; Rabeah, Jabor; Ludwig, Ralf; Neymeyr, Klaus; Seidel, Wolfram W.Alkyne complexes with vicinal substitution by a Lewis acid and a Lewis base at the coordinated alkyne are prospective frustrated Lewis pairs exhibiting a particular mutual distance and, hence, a specific activation potential. In this contribution, investigations on the generation of a WII alkyne complex bearing a phosphine as Lewis base and a carbenium group as Lewis acid are presented. Independently on potential substrates added, an intramolecular cyclisation product was always isolated. A subsequent deprotonation step led to an unprecedented side-on λ5-phosphinyne complex, which is interpreted as highly zwitterionic according to visible absorption spectroscopy supported by TD-DFT. Low-temperature 31P NMR and EPR spectroscopic measurements combined with time-dependent IR-spectroscopic monitoring provided insights in the mechanism of the cyclisation reaction. Decomposition of the multicomponent IR spectra by multivariate curve resolution and a kinetic hard-modelling approach allowed the derivation of kinetic parameters. Assignment of the individual IR spectra to potential intermediates was provided by DFT calculations. © 2020 The Authors. Published by Wiley-VCH GmbH
- ItemOn Silylated Oxonium and Sulfonium Ions and Their Interaction with Weakly Coordinating Borate Anions(Weinheim : Wiley-VCH, 2019) Bläsing, Kevin; Labbow, Rene; Michalik, Dirk; Reiß, Fabian; Schul, Axel; Villinger, Alexander; Walker, SvenjaAttempts have been made to prepare salts with the labile tris(trimethylsilyl)chalconium ions, [(Me3Si)3E]+ (E=O, S), by reacting [Me3Si-H-SiMe3][B(C6F5)4] and Me3Si[CB] (CB−=carborate=[CHB11H5Cl6]−, [CHB11Cl11]−) with Me3Si-E-SiMe3. In the reaction of Me3Si-O-SiMe3 with [Me3Si-H-SiMe3][B(C6F5)4], a ligand exchange was observed in the [Me3Si-H-SiMe3]+ cation leading to the surprising formation of the persilylated [(Me3Si)2(Me2(H)Si)O]+ oxonium ion in a formal [Me2(H)Si]+ instead of the desired [Me3Si]+ transfer reaction. In contrast, the expected homoleptic persilylated [(Me3Si)3S]+ ion was formed and isolated as [B(C6F5)4]− and [CB]− salt, when Me3Si-S-SiMe3 was treated with either [Me3Si-H-SiMe3][B(C6F5)4] or Me3Si[CB]. However, the addition of Me3Si[CB] to Me3Si-O-SiMe3 unexpectedly led to the release of Me4Si with simultaneous formation of a cyclic dioxonium dication of the type [Me3Si-μO-SiMe2]2[CB]2 in an anion-mediated reaction. DFT studies on structure, bonding and thermodynamics of the [(Me3Si)3E]+ and [(Me3Si)2(Me2(H)Si)E]+ ion formation are presented as well as mechanistic investigations on the template-driven transformation of the [(Me3Si)3E]+ ion into a cyclic dichalconium dication [Me3Si-μE-SiMe2]22+. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemMetal/Metal Redox Isomerism Governed by Configuration(Weinheim : Wiley-VCH, 2020) Ludwig, Stephan; Helmdach, Kai; Hettenschmidt, Mareike; Oberem, Elisabeth; Rabeah, Jabor; Villinger, Alexander; Ludwig, Ralf; Seidel, Wolfram W.A pair of diastereomeric dinuclear complexes, [Tp′(CO)BrW{μ-η2-C,C′-κ2-S,P-C2(PPh2)S}Ru(η5-C5H5)(PPh3)], in which W and Ru are bridged by a phosphinyl(thiolato)alkyne in a side-on carbon P,S-chelate coordination mode, were synthesized, separated and fully characterized. Even though the isomers are similar in their spectroscopic properties and redox potentials, the like-isomer is oxidized at W while the unlike-isomer is oxidized at Ru, which is proven by IR, NIR and EPR-spectroscopy supported by spectro-electrochemistry and computational methods. The second oxidation of the complexes was shown to take place at the metal left unaffected in the first redox step. Finally, the tipping point could be realized in the unlike isomer of the electronically tuned thiophenolate congener [Tp′(CO)(PhS)W{μ-η2-C,C′-κ2-S,P-C2(PPh2)S}Ru(η5-C5H5)-(PPh3)], in which valence trapped WIII/RuII and WII/RuIII cationic species are at equilibrium. © 2020 The Authors. Published by Wiley-VCH GmbH
- ItemSalts of HCN-Cyanide Aggregates : [CN(HCN)2]− and [CN(HCN)3]−(Weinheim : Wiley-VCH, 2020) Bläsing, Kevin; Harloff, Jörg; Schulz, Axel; Stoffers, Alrik; Stoer, Philip; Villinger, AlexanderAlthough pure hydrogen cyanide can spontaneously polymerize or even explode, when initiated by small amounts of bases (e.g. CN−), the reaction of liquid HCN with [WCC]CN (WCC=weakly coordinating cation=Ph4P, Ph3PNPPh3=PNP) was investigated. Depending on the cation, it was possible to extract salts containing the formal dihydrogen tricyanide [CN(HCN)2]− and trihydrogen tetracyanide ions [CN(HCN)3]− from liquid HCN when a fast crystallization was carried out at low temperatures. X-ray structure elucidation revealed hydrogen-bridged linear [CN(HCN)2]− and Y-shaped [CN(HCN)3]− molecular ions in the crystal. Both anions can be considered members of highly labile cyanide-HCN solvates of the type [CN(HCN)n]− (n=1, 2, 3 …) as well as formal polypseudohalide ions. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemHexacyanidosilicates with Functionalized Imidazolium Counterions(Weinheim : Wiley-VCH, 2020) Harloff, Jörg; Laatz, Karoline Charlotte; Lerch, Swantje; Schulz, Axel; Stoer, Philip; Strassner, Thomas; Villinger, AlexanderFunctionalized imidazolium cations were combined with the hexacyanidosilicate anion, [Si(CN)6]2–, by salt metathesis reactions with K2[Si(CN)6], yielding novel ionic compounds of the general formula [R–Ph(nBu)Im]2[Si(CN)6] {R = 2-Me (1), 4-Me (2), 2,4,6-Me = Mes (3), 2-MeO (4), 2,4-F (5), 4-Br (6); Im = imidazolium}. All synthesized imidazolium hexacyanidosilicates decompose upon thermal treatment above 95 °C (96 – 164 °C). Furthermore, the hexa-borane-adduct [Mes(nBu)Im]2{Si[(CN)B(C6F5)3]6}·6CH2Cl2 (7), which is thermally stable up to 215 °C, was obtained from the reaction of 3 with Lewis acidic B(C6F5)3. In CH3CN solution, decomposition of the hexaadduct to the Lewis-acid-base adduct CH3CN–B(C6F5)3 and [(C6F5)3B·(µ-CN)·B(C6F5)3]– was observed. All synthesized compounds were isolated in good yields and were completely characterized including single crystal structure elucidations. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemPalladium-catalyzed synthesis and nucleotide pyrophosphatase inhibition of benzo[4,5]furo[3,2-b]indoles(Frankfurt, Main : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2019) Do, Hoang Huy; Ullah, Saif; Villinger, Alexander; Lecka, Joanna; Sévigny, Jean; Ehlers, Peter; Iqbal, Jamshed; Langer, PeterA two-step palladium-catalyzed procedure based on Suzuki–Miyaura cross coupling, followed by a double Buchwald–Hartwig reaction, allows for the synthesis of pharmaceutically relevant benzo[4,5]furo[3,2-b]indoles in moderate to very good yield. The synthesized compounds have been analyzed with regard to their inhibitory activity (IC50) of nucleotide pyrophosphatases h-NPP1 and h-NPP3. The activity lies in the nanomolar range. The results were rationalized based on docking studies. © 2019 Do et al.