Acid–Base Free Main Group Carbonyl Analogues

Low-valent ( Me BDI)Al and ( Me BDI)Ga and highly Lewis acidic cations in [( tBu BDI)M + •C 6 H 6 ][(B(C 6 F 5 ) 4 À ]( M= Mg or Zn, Me BDI = HC[C(Me)N-DIPP] 2 , tBu BDI = HC[C-(tBu)N-DIPP] 2 ,D IPP = 2,6-diisopropylphenyl) react to heterobimetallic cations [( tBu BDI)Mg-Al( Me BDI) + ], [( tBu BDI)Mg-Ga( Me BDI) + ]a nd [( tBu BDI)Zn-Ga( Me BDI) + ]. These cations feature long Mg-Al (or Ga) bonds while the Zn-Ga bond is short. The [( tBu BDI)Zn-Al( Me BDI) + ]c ation was not formed. Combined AIM and charge calculations suggest that the metal-metal bonds to Zn are considerably more covalent, whereas those to Mg should be described as weak Al I (or Ga I )!Mg 2+ donor bonds.F ailure to isolate the Zn-Al combination originates from cleavage of the C À Fb ond in the solvent fluorobenzene to give ( tBu BDI)ZnPh and ( Me BDI)AlF + which is extremely Lewis acidic and was not observed, but ( Me BDI)Al(F)-(m-F)-(F)Al( Me BDI) + was verified by X-ray diffraction. DFT calculations show that the remarkably facile C-F bond cleavage follows adearomatization/rearomatization route.

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Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage

Friedrich

Eyselein

Langer

et al. 2021

Angewandte Chemie

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Synthesis, Structure, and Reactivity of Acid‐Free Neutral Oxoborane

et al. 2021

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An efficient synthesis of an acid‐free neutral oxoborane of the type carboranyl‐B(carbene)=O has been developed via a serendipitous discovery from the reaction of 1,2‐[BBr(carbene)]‐o‐carborane with AgOTf. This represents a new type of oxoborane. The stabilization of this oxoborane may be attributed to 1) kinetic stabilization provided by a bulky 3D carboranyl ligand and 2) thermodynamic stabilization offered by a carbene ligand. Crystallographic analyses support the presence of the shortest terminal B=O double bond ever reported thus far. Its reactivity has also been examined.

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Ein Boratafulven

2021

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Borole mit Bor‐gebundenen Alkylresten wurden hergestellt und charakterisiert und die Auswirkungen von Alkylsubstituenten auf die elektronischen Eigenschaften untersucht. Die Deprotonierung einer exozyklischen, Bor‐gebundenen Methylgruppe in einem B‐Methylborol führt zum 5‐Boratafulvenanion – einem Isomer des Boratabenzols. Das Boratafulven wurde charakterisiert, und die elektronischen Eigenschaften wurden durch DFT‐Rechnung untersucht. Eine computerchemische Abschätzung der pKs‐Werte der exozyklischen B‐CH3‐Gruppen für Substitutionsderivate des Borols weist auf eine erhöhte C‐H‐Azidität infolge des in einen antiaromatischen Ring eingebetteten Boratoms hin. Das nicht‐aromatische Boratafulven reagiert als C‐zentriertes Nukleophil mit dem milden Elektrophil Me3SnCl, unter Zurückgewinnung des antiaromatischen Charakters, zu einem Stannylmethylborol. Als nukleophile Synthone für Borole eröffnen Boratafulvene einen neuen Zugang zu diesen hochreaktiven Heterozyklen. Das Boratafulven reagiert gegenüber Benzophenon als Methylen‐Transferreagenz in einer bora‐Wittig‐artigen Reaktion unter Bildung eines Boroloxids.

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Acid–Base Free Main Group Carbonyl Analogues

Abstract: Scheme 1. Main group carbonyl analogues of types I and II.

Cited by 11 publications

References 130 publications

Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage

Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage

Synthesis, Structure, and Reactivity of Acid‐Free Neutral Oxoborane

Ein Boratafulven

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