The 9‐Borataphenanthrene Anion

A series of linear late transition metal (M=Cu, Ag, Au and Zn) complexes featuring a side‐on [B=C]− containing ligand have been isolated and characterised. The [B=C]− moiety is isoelectronic with the C=C system of an alkene. Comparison across the series shows that in the solid‐state, deviation between the η2 and η1 coordination mode occurs. A related zinc complex containing two [B=C]− ligands was prepared as a further point of comparison for the η1 coordination mode. The bonding in these new complexes has been interrogated by computational techniques (QTAIM, NBO, ETS‐NOCV) and rationalised in terms of the Dewar–Chatt–Duncanson model. The combined structural and computational data provide unique insight into catalytically relevant linear d10 complexes of Cu, Ag and Au. Slippage is proposed to play a key role in catalytic reactions of alkenes through disruption and polarisation of the π‐system. Through the preparation and analysis of a consistent series of group 11 complexes, we show that variation of the metal can impact the coordination mode and hence substrate activation.

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Group 11 Borataalkene Complexes: Models for Alkene Activation

Phillips

Kong

White

et al. 2021

Angewandte Chemie

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Stabilization of the Elusive 9‐Carbene‐9‐Borafluorene Monoanion

et al. 2021

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Two-electron reduction of carbene-supported 9bromo-9-borafluorenes with excess KC 8 , Na, or Li-naphthalenide affords six N-heterocyclic carbene (NHC)-or cyclic-(alkyl)(amino) carbene (CAAC)-stabilized borafluorene anions (3-8)-the first isolated and structurally authenticated examples of the elusive 9-carbene-9-borafluorene monoanion. The electronic structure, bonding, and aromaticity of the boracyclic anions were comprehensively investigated via computational studies. Compounds 5 and 8 react with metal halides via salt elimination to give new B-E (E = Au, Se, Ge)containing materials (9-12). Upon reaction with diketones, the carbene ligand cleanly dissociates from 5 or 8 to yield new B-O containing spirocycles (13-14) that cannot be easily obtained using "normal" valent borafluorene compounds. Collectively, these results support the notion that carbene-stabilized monoanionic borafluorenes may serve as a new platform for the onestep construction of higher-value boracyclic materials.

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Formation and Cycloaddition Reactions of a Reactive Boraalkene Stabilized Internally by N‐Heterocyclic Carbene

et al. 2021

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The synthesis of element−carbon double bonds is of great importance for the development and understanding of reactive π‐bonded systems in chemistry. The seven‐membered heterocyclic system 4 b is readily made by internal C−H activation at a pendent isopropyl methyl group of the respective [(IPr)C6F5BH]+ borenium ion. Subsequent deprotonation with the IMes carbene gives the neutral cyclic boraalkene system 5 b. The B=C double bond in compound 5 b adds carbon dioxide, CS2, sulfur dioxide, phenyl isocyanate, an acetylenic ester or two NO molecules to give the corresponding four‐membered ring annulated heterocycles. With sulfur or selenium 5 b gives the respective three‐membered ring systems. N2O reacts with 5 b to give a mixture of the related oxaborirane 18 and a unique [B]OH containing diazoalkane product 19.

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The 9‐Borataphenanthrene Anion

Cited by 10 publications

References 96 publications

Group 11 Borataalkene Complexes: Models for Alkene Activation

Group 11 Borataalkene Complexes: Models for Alkene Activation

Stabilization of the Elusive 9‐Carbene‐9‐Borafluorene Monoanion

Formation and Cycloaddition Reactions of a Reactive Boraalkene Stabilized Internally by N‐Heterocyclic Carbene

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