“Umpolung” at Boron by Reduction of [B(CN)4]− and Formation of the Dianion [B(CN)3]2−

Bernhardt, Eduard; Bernhardt‐Pitchougina, Vera; Willner, Helge; Ignatíev, Nikolai

doi:10.1002/anie.201105848

Cited by 82 publications

(105 citation statements)

References 39 publications

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“…TheI Ra nd Raman spectra of the potassium salts of 10 B and 11 Bl abeled and non-labeled 1 are shown in Figure 3d. Theassignment of the bands observed is based on acomparison to calculated displacement vectors, 10 B/ 11 Bisotopic shifts, and the selection rule (Table S2).…”

Section: Methodsmentioning

confidence: 99%

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The Hexacyanodiborane(6) Dianion [B₂(CN)₆]²⁻

et al. 2015

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Diborane(6) dianions with substituents that are bonded to boron via carbon are very reactive and therefore only a few examples are known. Diborane(6) derivatives are the simplest catenated boron compounds with an electron-precise B-B σ-bond that are of fundamental interest and of relevance for material applications. The homoleptic hexacyanodiborane(6) dianion [B2 (CN)6 ](2-) that is chemically very robust is reported. The dianion is air-stable and resistant against boiling water and anhydrous hydrogen fluoride. Its salts are thermally highly stable, for example, decomposition of (H3 O)2 [B2 (CN)6 ] starts at 200 °C. The [B2 (CN)6 ](2-) dianion is readily accessible starting from 1) B(CN)3 (2-) and an oxidant, 2) [BF(CN)3 ](-) and a reductant, or 3) by the reaction of B(CN)3 (2-) with [BHal(CN)3 ](-) (Hal=F, Br). The latter reaction was found to proceed via a triply negatively charged transition state according to an SN 2 mechanism.

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Section: Methodsmentioning

confidence: 99%

“…[11] In addition to the well-defined anions 2 and 3,af ew further homoleptic cyano boron species are known. [11] In addition to the well-defined anions 2 and 3,af ew further homoleptic cyano boron species are known.…”

Section: àmentioning

confidence: 99%

The Hexacyanodiborane(6) Dianion [B₂(CN)₆]²⁻

et al. 2015

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“…Although a rich and varied chemistry has since arisen from the reactivity of compound 1 and related N- heterocyclic boryl anions with organic914, transition metal15161718 and main group electrophiles1419202122232425, alternative nucleophilic boron reagents remain very rare species262728293031. Notable exceptions are Braunschweig's dimetalloborylene and borolyl anions (for example, 2 and 3 )3233 Bertrand and Kinjo's carbene-stabilised monovalent boron species (for example, 4 )3435363738 and a remarkable tricyanoborandiyl dianion394041. Although the transient generation of {BH 2 } − anion equivalents has also been achieved within the coordination sphere of 1,3-bis-(2,6-diisopropyl-phenyl)imidazol-2-ylidene42, the syntheses of all these species require strongly reducing and potentially problematic reaction conditions (for example, Li metal or C 8 K) to achieve the formal B(I) oxidation state.…”

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Easy access to nucleophilic boron through diborane to magnesium boryl metathesis

et al. 2017

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Organoboranes are some of the most synthetically valuable and widely used intermediates in organic and pharmaceutical chemistry. Their synthesis, however, is limited by the behaviour of common boron starting materials as archetypal Lewis acids such that common routes to organoboranes rely on the reactivity of boron as an electrophile. While the realization of convenient sources of nucleophilic boryl anions would open up a wealth of opportunity for the development of new routes to organoboranes, the synthesis of current candidates is generally limited by a need for highly reducing reaction conditions. Here, we report a simple synthesis of a magnesium boryl through the heterolytic activation of the B–B bond of bis(pinacolato)diboron, which is achieved by treatment of an easily generated magnesium diboranate complex with 4-dimethylaminopyridine. The magnesium boryl is shown to act as an unambiguous nucleophile through its reactions with iodomethane, benzophenone and N,N′-di-isopropyl carbodiimide and by density functional theory.

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“…B(CO 2 H) 4 − (Bernhardt et al 2006), and a hydrogenated one, e.g. BH 2 (CN 2 ) (Györi et al 1983), as well as a dianion B(CN) 3 2− (Bernhardt et al 2011) that could change the accessibility of the molecule for enzymatic attack.…”

Section: Discussionmentioning

confidence: 99%

Biodegradation potential of cyano-based ionic liquid anions in a culture of Cupriavidus spp. and their in vitro enzymatic hydrolysis by nitrile hydratase

Neumann

Pawlik

Bryniok

et al. 2013

Environ Sci Pollut Res

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Biodegradation tests with bacteria from activated sludge revealed the probable persistence of cyano-based ionic liquid anions when these leave waste water treatment plants. A possible biological treatment using bacteria capable of biodegrading similar compounds, namely cyanide and cyano-complexes, was therefore examined. With these bacteria from the genera Cupriavidus, the ionic liquid anions B(CN)4−, C(CN)3−, N(CN)2− combined with alkaline cations were tested in different growth media using ion chromatography for the examination of their primary biodegradability. However, no enhanced biodegradability of the tested cyano-based ionic liquids was observed. Therefore, an in vitro enzymatic hydrolysis test was additionally run showing that all tested ionic liquid (IL) anions can be hydrolysed to their corresponding amides by nitrile hydratase, but not by nitrilase under the experimental conditions. The biological stability of the cyano-based anions is an advantage in technological application, but the occurrence of enzymes that are able to hydrolyse the parent compound gives a new perspective on future cyano-based IL anion treatment.

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“Umpolung” at Boron by Reduction of [B(CN)₄]⁻ and Formation of the Dianion [B(CN)₃]²⁻

Cited by 82 publications

References 39 publications

The Hexacyanodiborane(6) Dianion [B₂(CN)₆]²⁻

The Hexacyanodiborane(6) Dianion [B₂(CN)₆]²⁻

Easy access to nucleophilic boron through diborane to magnesium boryl metathesis

Biodegradation potential of cyano-based ionic liquid anions in a culture of Cupriavidus spp. and their in vitro enzymatic hydrolysis by nitrile hydratase

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“Umpolung” at Boron by Reduction of [B(CN)4]− and Formation of the Dianion [B(CN)3]2−

Cited by 82 publications

References 39 publications

The Hexacyanodiborane(6) Dianion [B2(CN)6]2−

The Hexacyanodiborane(6) Dianion [B2(CN)6]2−

Easy access to nucleophilic boron through diborane to magnesium boryl metathesis

Biodegradation potential of cyano-based ionic liquid anions in a culture of Cupriavidus spp. and their in vitro enzymatic hydrolysis by nitrile hydratase

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“Umpolung” at Boron by Reduction of [B(CN)₄]⁻ and Formation of the Dianion [B(CN)₃]²⁻

The Hexacyanodiborane(6) Dianion [B₂(CN)₆]²⁻

The Hexacyanodiborane(6) Dianion [B₂(CN)₆]²⁻