Bulky derivatives of boranes, boronic acids and boronate estersvia reaction with diazomethanes

Neu, Rebecca C.; Jiang, Chunfang; Stephan, Douglas W.

doi:10.1039/c2dt31868g

Cited by 53 publications

(43 citation statements)

References 89 publications

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“…Based on multinuclear NMR spectroscopy and literature data on related organoboron compounds,25 we conclude that 3 contains a (C 6 F 5 )B−C(H)(C 6 F 5 ) 2 fragment as well as a siloxyborate linkage. DFT calculated and benchmarked NMR chemical shifts support the presence of a four‐coordinated B‐nucleus with an additional pyridine→boron interaction, as in 3 (Scheme 3 and the Supporting Information).…”

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confidence: 74%

Transition‐Metal‐Free Cleavage of CO

Devillard

Bruin

Siegler

et al. 2017

Chemistry A European J

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Tertiary silane 1H, 2‐[(diphenylsilyl)methyl]‐6‐methylpyridine, reacts with tris(pentafluorophenyl)borane (BCF) to form the intramolecular pyridine‐stabilized silylium 1+‐HBCF. The corresponding 2‐[(diphenylsilyl)methyl]pyridine, lacking the methyl‐group on the pyridine ring, forms classic N(py)→B adduct 2H‐BCF featuring an intact silane Si−H fragment. Complex 1+‐HBCF promotes cleavage of the C≡O triple bond in carbon monoxide with double C−Csp2 bond formation, leading to complex 3 featuring a B‐(diarylmethyl)‐B‐aryl‐boryloxysilane fragment. Reaction with pinacol generates bis(pentafluorophenyl)methane 4 as isolable product, proving the transition‐metal‐free deoxygenation of carbon monoxide by this main‐group system. Experimental data and DFT calculations support the existence of an equilibrium between the silylium–hydroborate ion pair and the silane–borane mixture that is responsible for the observed reactivity.

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confidence: 74%

Transition‐Metal‐Free Cleavage of CO

Devillard

Bruin

Siegler

et al. 2017

Chemistry A European J

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“…[144,155] Ty pical examples include [( F RO) 3 Al-X-Al-(OR F ) 3 ) 2 ] À X = F, [142] Cl, [145] X = OH; [146] [155] and [Ph 3 [155] Fort he Synthesis of Reactive Cations:W ei nclude some recent and exemplary examples highlighting this approach for the formation of reactive cations.S imple halide abstraction from the ruthenium fluoride complexes [Ru(L) 2 (CO) 2 F 2 ] (where L = PPh 3 or NHC) by the Lewis acids BF 3 ,P F 5 ,a nd B(C 6 F 5 ) 3 gives the corresponding fluoride-containing WCAs. [204,205] Them olecular dimer Al 2 Br 6 has been shown to abstract bromide from tert-butyl bromide to form the room temperature stable [ t Bu][Al 2 Br 7 ]s alt, which has am elting point of 2 8 8C, thus making it ar oom-temperature ionic liquid. [216] [203] (top left) and selected examples of novel B(C 6 F 5 )RR' Lewis acids (right and bottom).…”

Section: Strong Lewis Acidsmentioning

confidence: 99%

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

et al. 2018

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This Review gives a comprehensive overview of the most topical weakly coordinating anions (WCAs) and contains information on WCA design, stability, and applications. As an update to the 2004 review, developments in common classes of WCA are included. Methods for the incorporation of WCAs into a given system are discussed and advice given on how to best choose a method for the introduction of a particular WCA. A series of starting materials for a large number of WCA precursors and references are tabulated as a useful resource when looking for procedures to prepare WCAs. Furthermore, a collection of scales that allow the performance of a WCA, or its underlying Lewis acid, to be judged is collated with some advice on how to use them. The examples chosen to illustrate WCA developments are taken from a broad selection of topics where WCAs play a role. In addition a section focusing on transition metal and catalysis applications as well as supporting electrolytes is also included.

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“…[31,[33][34][35][36][37] Once the release of N 2 had stopped upon warming to 20 8 8C, the solvent was removed, affording aminoborane [H(C 6 F 5 )NÀB(C 6 F 5 ) 2 ](2H). [38] The transfer of aC 6 F 5 group from boron to another main group element was also observed in the decomposition of the adduct formed between abis(amino)silylene and B(C 6 F 5 ) 3 within one month. X-ray diffraction experiments revealed the migration of one C 6 F 5 group from the boron to the nitrogen atom upon release of N 2 , in accord with solution NMR studies (see Figure S7 and Table S1).…”

mentioning

confidence: 99%