Using the Secondary PH/BH Functional Groups of an Active Geminal Frustrated Lewis Pair for Carbon Monoxide Reduction and Reactions with Nitriles and Isonitriles

The Mes2P‐C≡C‐SiMe3 alkyne reacts with the borane H2B‐Fmes by means of a rare 1,1‐hydroboration reaction to give an unsaturated C2‐bridged frustrated P/B‐H Lewis pair. Most of its reactions are determined by the presence of the B‐H functionality at the FLP function and the activated connecting carbon‐carbon double bond. It reduces carbon monoxide to the formyl stage. With nitriles it reacts in an extraordinary way: it undergoes a reaction sequence that eventually results in the formation of a P‐substituted dihydro‐1,2‐azaborole derivative. Several similar examples were found. In one case a P‐ylide was isolated that was related to an intermediate of the reaction sequence. It subsequently opened in an alternative way to give an alkenyl borane product.

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Alkyne 1,1‐Hydroboration to a Reactive Frustrated P/B‐H Lewis Pair

Škoch

Daniliuc

Kehr

et al. 2021

Angewandte Chemie

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Colorimetric Metal‐Free Detection of Carbon Monoxide: Reversible CO Uptake by a BNB Frustrated Lewis Pair

et al. 2021

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We report two BNB-type frustrated Lewis pairs which feature an acceptor-donor-acceptor functionalized cavity, and which differ in the nature of the B-bound fluoroaryl group (C 6 F 5 vs. C 6 H 3 (CF 3 ) 2 -3,5, Ar f ). These receptor systems are capable of capturing gaseous CO, and in the case of the -BAr f 2 system this can be shown to occur in reversible fashion at/above room temperature. For both systems, the binding event is accompanied by migration of one of the aryl substituents to the electrophilic carbon of the CO guest. Experiments utilizing an additional equivalent of P t Bu 3 allow the initially formed (non-migrated) CO adduct to be identified and trapped (via demethylation), while also establishing the reversibility of the B-to-C migration process. When partnered with the slightly less Lewis acidic -BAr f 2 substituent, this reversibility allows for release of the captured carbon monoxide in the temperature range 40-70 8C, and the possibility for CO sensing, making use of the associated colourless to orange/ red colour change.

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Three‐Component Reaction to 1,4,2‐Diazaborole‐Type Heteroarene Systems

Erker

Daniliuc

et al. 2021

Angewandte Chemie

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The borane FmesBH 2 reacts in at hree-component reaction with an isonitrile and asmall series of organonitriles to give rare examples of the class of dihydro-1,4,2-diazaborole derivatives.I narelated way,a nnulated BN-indolizine derivatives became conveniently available,a sw ere dihydro-1,4,2oxaza-or thiazaborole derivatives.T he nucleophilic framework of ad ihydro-1,4,2-diazaborole example allowed for an uncatalyzed acylation reaction. It also served as a1 ,3-dipolar reagent and underwent a[ 3 + +2] cycloaddition/[4+ +2] cycloreversion sequence when treated with methyl propiolate to give the respective pyrrole product. The [3+ +2] cycloaddition product of ad ihydro-1,4,2-diazaborole derivative with Nphenylmaleimide was isolated and its heterobicyclo-[2.2.1]heptane derived structure characterized by X-ray diffraction.

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Using the Secondary PH/BH Functional Groups of an Active Geminal Frustrated Lewis Pair for Carbon Monoxide Reduction and Reactions with Nitriles and Isonitriles

Cited by 8 publications

References 75 publications

Alkyne 1,1‐Hydroboration to a Reactive Frustrated P/B‐H Lewis Pair

Alkyne 1,1‐Hydroboration to a Reactive Frustrated P/B‐H Lewis Pair

Colorimetric Metal‐Free Detection of Carbon Monoxide: Reversible CO Uptake by a BNB Frustrated Lewis Pair

Three‐Component Reaction to 1,4,2‐Diazaborole‐Type Heteroarene Systems

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