Stoichiometric Metal-Free Reduction of CO in Syn-Gas

Dobrovetsky, Roman; Stephan, Douglas W.

doi:10.1021/ja401492s

Cited by 146 publications

(96 citation statements)

References 47 publications

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“…Compound 165 is formed by hydrogenation of 164 whereas 166 was formed by carbonylation (Scheme 55). [122] The elusive formylborane 162 was removed from the FLP template of compound 161 by treatment with excess pyridine and the stable pyridine adduct 167 was isolated and characterized by X-ray diffraction (Scheme 56). This adduct 167 undergoes a variety of typical carbaldehyde reactions, such as Wittig olefination or chromate(VI) oxidation to the corresponding vinylborane or borane carboxylic acid, respectively.…”

Section: Bhmentioning

confidence: 99%

Frustrated Lewis Pair Chemistry: Development and Perspectives

2015

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Frustrated Lewis pairs (FLPs) are combinations of Lewis acids and Lewis bases in solution that are deterred from strong adduct formation by steric and/or electronic factors. This opens pathways to novel cooperative reactions with added substrates. Small-molecule binding and activation by FLPs has led to the discovery of a variety of new reactions through unprecedented pathways. Hydrogen activation and subsequent manipulation in metal-free catalytic hydrogenations is a frequently observed feature of many FLPs. The current state of this young but rapidly expanding field is outlined in this Review and the future directions for its broadening sphere of impact are considered.

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Section: Bhmentioning

confidence: 99%

Frustrated Lewis Pair Chemistry: Development and Perspectives

2015

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“…The calculated mechanism of the reaction suggests that the two Lewis acidic borylene boron atoms cooperate to cleave the CÀOm ultiple bond with minimal influence from the metal center, afeature reminiscent of the CÀOcleavage reported by Stephan in 2013. [4] Them echanism also hinges on the partial transfer of aC Ol igand from the metal to an arylborylene ligand, aphenomenon that also forms the basis of our recent work on borylene-CO coupling and the liberation of monovalent boron species from metal scaffolds,i ncluding our recent syntheses of boraketenes,boraketenimines,and aborylene dicarbonyl. [21] …”

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Mild and Complete Carbonyl Ligand Scission on a Mononuclear Transition Metal Complex

et al. 2016

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The complete scission of the carbon-oxygen bond of carbon monoxide, while frequently observed on bulk metals and with bimetallic and cluster transition metal complexes, is unknown with monometallic systems. Reaction of a zerovalent iron bis(borylene) complex with a cyclic (alkyl)(amino)carbene revealed a highly selective intramolecular cleavage of the C-O bond of a carbonyl ligand at room temperature, leading to the formation of a highly unusual iron complex containing a base-stabilized (bora)alkylideneborane ligand. DFT investigation of the reaction mechanism suggested that the two Lewis acidic borylene boron atoms cooperate to cleave the C-O multiple bond.

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“…[10] Highly Lewis acidic pentaphenylborole (BC4Ph5) was found to coordinate CO at boron before undergoing CO insertion into the borole ring. [11] This borole was also found to undergo H2 addition to the two endocyclic carbon atoms adjacent to boron.…”

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Reactivity of a Dihydrodiborene with CO: Coordination, Insertion, Cleavage, and Spontaneous Formation of a Cyclic Alkyne

et al. 2017

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Under a CO atmosphere the dihydrodiborene [(cAAC)HB=BH(cAAC)] underwent coordination of CO concomitant with reversible hydrogen migration from boron to the carbene carbon atom, as well as reversible CO insertion into the B=B bond. Heating of the CO-adduct resulted in two unusual cAAC ring-expansion products, one presenting a B=C bond to a six-membered 1,2-azaborinane-3-ylidene, the other an unprecedented nine-membered cyclic alkyne resulting from reductive cleavage of CO and spontaneous C≡C triple bond formation.

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Stoichiometric Metal-Free Reduction of CO in Syn-Gas

Cited by 146 publications

References 47 publications

Frustrated Lewis Pair Chemistry: Development and Perspectives

Frustrated Lewis Pair Chemistry: Development and Perspectives

Mild and Complete Carbonyl Ligand Scission on a Mononuclear Transition Metal Complex

Reactivity of a Dihydrodiborene with CO: Coordination, Insertion, Cleavage, and Spontaneous Formation of a Cyclic Alkyne

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