Protonierung kontra Oxoniumsalz‐Bildung: Abstimmung der Basizität und Stabilität von Cyanoborat‐Anionen

Kerpen, Christoph; Sprenger, Jan A. P.; Herkert, Lorena; Schäfer, Marius; Bischoff, Lisa A.; Zeides, Pierre; Grüne, Matthias; Bertermann, Rüdiger; Brede, Franziska A.; Müller‐Buschbaum, Klaus; Ignat’ev, Nikolai; Finze, Maik

doi:10.1002/ange.201611901

Cited by 17 publications

(16 citation statements)

References 37 publications

(32 reference statements)

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“…[6] Furthermore, in recent years other cyanoborate-ILs were developed, [6] which include ILs with cyanohydridoborate anions [BH n (CN) 4Àn ] À (n = 1-3) [16] and perfluoroalkylcyano(fluoro)borate anions [R F BF n (CN) 3Àn ] À (n = 0-2). [17] Cyano(fluoro)borate anions have been used as weakly coordinating counteranions for the stabilization of reactive cations, such as {H(H 2 O) x } + (x = 0-2) [18][19][20] or Ph 3 C + [21] , and as ligands in metal coordination chemistry. [6] Especially the tetracyanoborate ([B(CN) 4 ] À , TCB) and the tricyanofluoroborate anion ([BF(CN) 3 ] À , MFB) are in the focus of current research.…”

Section: Introductionmentioning

confidence: 99%

“…The main reason is that they are the most stable anions in the series TCB, MFB, DFB, and [BF 3 (CN)] À . [5,7,22,23] This is obvious from a comparison of their stability against the oxonium ion; (H 3 O)[B(CN) 4 ] [18,19] and (H 3 O)[BF(CN) 3 ] [18,20] are stable in the solid and in solution, whereas (H 3 O)[BF 2 (CN) 2 ] is stable in solution, only, [18] and (H 3 O)[BF 3 (CN)] decomposes even in aqueous solution. Examples for coordination compounds with the TCB and MFB ion include main group metal salts [24] and transition metal [8,25,26,27] as well as lanthanide complexes.…”

Section: Introductionmentioning

confidence: 99%

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Innovative Syntheses of Cyano(fluoro)borates: Catalytic Cyanation, Electrochemical and Electrophilic Fluorination

Drisch

Bischoff

Sprenger

et al. 2020

Chemistry A European J

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Different types of high‐yield, easily scalable syntheses for cyano(fluoro)borates Kt[BFn(CN)4−n] (n=0–2) (Kt=cation), which are versatile building blocks for materials applications and chemical synthesis, have been developed. Tetrafluoroborates react with trimethylsilyl cyanide in the presence of metal‐free Brønsted or Lewis acid catalysts under unprecedentedly mild conditions to give tricyanofluoroborates or tetracyanoborates. Analogously, pentafluoroethyltrifluoroborates are converted into pentafluoroethyltricyanoborates. Boron trifluoride etherate, alkali metal salts, and trimethylsilyl cyanide selectively yield dicyanodifluoroborates or tricyanofluoroborates. Fluorination of cyanohydridoborates is the third reaction type that includes direct fluorination with, for example, elemental fluorine, stepwise halogenation/fluorination reactions, and electrochemical fluorination (ECF) according to the Simons process. In addition, fluorination of [BH(CN)2{OC(O)Et}]− to result in [BF(CN)2{OC(O)Et}]− is described.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Innovative Syntheses of Cyano(fluoro)borates: Catalytic Cyanation, Electrochemical and Electrophilic Fluorination

Drisch

Bischoff

Sprenger

et al. 2020

Chemistry A European J

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“…H[BH 2 (CN) 2 ]w as prepared as reported in the literature. [22] Anhydrous acetonitrile (Sigma-Aldrich, 99.8 %) and pyridine (Acros, 99.0 %) were used as purchased. The respective lanthanide chlorides were mixed with either anhydrous acetonitrile (1-3)o ra nhydrous pyridine (4 and 5)a nd sealed in evacuated glass ampoules (1 10 À3 mbar) through Quickfit techniques, and degassed three times by freezing with liquid nitrogen.…”

Section: Methodsmentioning

confidence: 99%

“…The reported lanthanide cyanoborates 1-5 were synthesized from anhydrous lanthanide chlorides and H[BH 2 (CN) 2 ] [22] in either anhydrous acetonitrile (1-3)o rp yridine (4 and 5), accompanied by the formationo fH Cl as the side product of the acid-base reactions. For the MOFs 1-3,acomplete substitution of chloride ions is observed, whereas the strand-like compounds 4 and 5 exhibit only ap artial substitution of chloride ions.…”

Section: Synthesesmentioning

confidence: 99%

“…Remarkably,both solvents take part in the product formation:p yridine in coordination and the charge compensation by [H(py) 2 ] + in 4 and 5,a nd acetonitrile coordinating the intercalated complex cations [Ln(CH 3 CN) 9 ] 3 + for charge compensation in the frameworks 1-3.T he reactiont emperature for the reported syntheses was set between 80 8Cf or 1-3 and1 00 8Cf or 4 and 5,d ue to the limited thermal stabilityo fH [BH 2 (CN) 2 ]. [22]…”

Section: Synthesesmentioning

confidence: 99%

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Lanthanide Coordination Polymers and MOFs based on the Dicyanodihydridoborate Anion

Zottnick

Daul

Kerpen

et al. 2018

Chemistry A European J

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New lanthanide cyanoborates were synthesized from anhydrous lanthanide chlorides and the acid H[BH (CN) ] in either acetonitrile or pyridine. Reactions in acetonitrile lead to three-dimensional, anionic metal-organic frameworks (MOFs) [Ln {BH (CN) } ]⋅[Ln(CH CN) ] (Ln=Ce, Eu, Tb) which incorporate complex cations [Ln(CH CN) ] in the pores of the framework for charge compensation. In contrast, the reactions in pyridine result in the formation of one-dimensional coordination polymers [H(py) ][LnCl {BH (CN) } (py) ]⋅0.5 py (Ln=Ce, Pr, py=pyridine) with [H(py) ] as counter ions for the anionic strand structure. The products show intense photoluminescence, for Ce based on 5d-4f transitions in the blue spectral region, whereas the Eu and Tb compounds exhibit characteristic photoluminescence based on 4f-4f transitions of the respective lanthanide ions. The observed photoluminescence is mainly attributed to a direct excitation of the lanthanide ions and sensitization of the lanthanide ions by the [BH (CN) ] anions. These results mark the utilized borate anions as versatile building block for new coordination compounds.

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Bor in energiebezogenen Prozessen und Anwendungen

et al. 2020

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Direkt an der Grenze zwischen Metallen und Nichtmetallen angesiedelt, nimmt das Element Bor eine einzigartige Position im Periodensystem ein. Diese besondere Stellung ermöglicht eine enorme Vielfalt an chemischen Reaktionen und Anwendungen. Auch in Hinblick auf die stetig steigende Nachfrage an erneuerbaren und sauberen Energien bzw. energieeffizienten Prozessen ist das Element Bor mehr und mehr in den Fokus der energiebezogenen Forschung gerückt und umfasst mittlerweile Bereiche wie 1) die Aktivierung und Synthese kleiner energiereicher Moleküle, 2) die Speicherung von chemischer und elektrischer Energie und 3) die Umwandlung von elektrischer Energie zu Licht. Diese Anwendungen basieren hierbei auf den besonderen Eigenschaften des Elements Bor, d. h. vor allem auf dessen Elektronenmangel in Verbindung mit der Gegenwart eines unbesetzten p‐Orbitals, was die Ausbildung unzähliger Verbindungen mit gezielt beeinflussbaren chemischen und physikalischen Eigenschaften ermöglicht. So erreicht Bor beispielsweise mit vier kovalenten Bindungen und einer negativen Ladung relativ einfach ein Elektronenoktett, wodurch die Verbindungsklasse der Boratanionen zugänglich wird, welche eine außergewöhnlich hohe chemische und elektrochemische Stabilität aufweisen. Besonders hervorzuheben ist in diesem Zusammenhang die synthetisch wertvolle Klasse der schwach‐koordinierenden Anionen. Dieser Aufsatz soll die Bedeutung von Borverbindungen für energiebezogene Prozesse und Anwendungen verdeutlichen und fasst die Fortschritte der letzten Jahre auf diesem Gebiet zusammen.

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Protonierung kontra Oxoniumsalz‐Bildung: Abstimmung der Basizität und Stabilität von Cyanoborat‐Anionen

Abstract: Wasserfreies H[BH 2 (CN) 2 ]k ristallisiert aus sauren wässrigen Lçsungen des Dicyanodihydridoborat-Anions.

Cited by 17 publications

References 37 publications

Innovative Syntheses of Cyano(fluoro)borates: Catalytic Cyanation, Electrochemical and Electrophilic Fluorination

Innovative Syntheses of Cyano(fluoro)borates: Catalytic Cyanation, Electrochemical and Electrophilic Fluorination

Lanthanide Coordination Polymers and MOFs based on the Dicyanodihydridoborate Anion

Bor in energiebezogenen Prozessen und Anwendungen

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