Single and double activation of acetone by isolobal BN and BB triple bonds

Böhnke, Julian; Brückner, Tobias; Hermann, Alexander; González-Belman, Oscar F.; Arrowsmith, Merle; Jiménez‐Halla, J. Óscar C.; Braunschweig, Holger

doi:10.1039/c8sc01249k

Cited by 39 publications

(49 citation statements)

References 35 publications

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“…Köppe and Schnöckel questioned this triple bond based on electronic interactions between the B−B bond and the two B−(NHC) bonds . However, later Grunenberg's and Frenking's calculations, Braunschweig's Raman and NMR spectroscopic measurements as well as chemical reactions, supported the existence of the B≡B triple bond in NHC→B≡B←NHC.…”

Section: Figurementioning

confidence: 99%

Realization of an Al≡Al Triple Bond in the Gas‐Phase Na₃Al₂⁻ Cluster via Double Electronic Transmutation

et al. 2018

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The discovery of homodinuclear multiple bonds composed of Group 13 elements represents one of the most challenging frontiers in modern chemistry. A classical triple bond such as N≡N and HC≡CH contains one σ bond and two π bonds constructed from the p orbitals perpendicular to the σ bond. However, the traditional textbook triple bond between two Al atoms has remained elusive. Here we report an Al≡Al triple bond in the designer Na Al cluster predicted in silico, which was subsequently generated by pulsed arc discharge followed by mass spectrometry and photoelectron spectroscopy characterizations. Being effectively Al due to the electron donation from Na, the Al atoms in Na Al undergo a double electronic transmutation into Group 15 elements, thus the Al ≡Al kernel mimics the P≡P and N≡N molecules. We anticipate this work will stimulate more endeavors in discovering materials using Al ≡Al as a building block in the gas phase and in the solid state.

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Section: Figurementioning

confidence: 99%

Realization of an Al≡Al Triple Bond in the Gas‐Phase Na₃Al₂⁻ Cluster via Double Electronic Transmutation

et al. 2018

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“…C−H activation on multiple bonds to group 13 elements is much less common and is usually manifested by the addition of C−H acidic substrates. Thus, the group of Braunschweig demonstrated the addition of acetone to B≡N and B≡B triple bonds, such as in 8 . Inoue et al.…”

Section: Introductionmentioning

confidence: 99%

Sequential Oxidation and C−H Bond Activation at a Gallium(I) Center

et al. 2019

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In situ oxidation of the GaI compound NacNacGa by either N2O or pyridine oxide results in the generation of a labile monomeric oxide, NacNacGa(O), which can easily cleave the C−H bonds of aliphatic and aromatic substrates featuring good donor sites. The products of this reaction are gallium organyl hydroxides. DFT calculations show that these reactions start with the formation of NacNac‐Ga(O)(L) adducts, the oxo ligand of which can easily abstract protons from nearby C−H bonds, even for sp2‐hybridized carbon centers. Aliphatic amines do not enter this reaction for kinetic reasons, presumably because of the unfavorable sterics.

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“…Even more than diborenes, diborynes species possess a rich reactivity, including interactions with chalcogens, dichalcogenides, 199,201 isocyanides 202 and acetone. 203 In contrast to diborenes, the metallomimetic reactivity of diborynes is more clearly exemplified. Indeed, [IDippB]2 (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) (12) reacts rapidly with one equivalent of CO to give bridging adduct 13 (Figure 13, B).…”

Section: Metallomimetic Chemistry Of B-b Bondsmentioning

confidence: 99%

Metallomimetic Chemistry of Boron

2019

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The study of main-group molecules that behave and react similarly to transition metal (TM) complexes has attracted significant interest in the recent decades. Most notably, the attractive idea of eliminating the all-too-often rare and costly metals from catalysis has motivated efforts to develop main-group-element-mediated reactions. Main-group elements, however, lack the electronic flexibility of many TM complexes that arise from combinations of empty and filled d-orbitals and that seem ideally suited to bind and activate many substrates. In this Review, we look at boron, an element which, despite its non-metal nature, low atomic weight, and relative redox staticity has achieved great milestones in terms of TM-like reactivity. We show how in inter-element cooperative systems, diboron molecules and hypovalent complexes, the fifth element can acquire a truly metallomimetic character. As we discuss, this character is particularly strikingly demonstrated by the reactivity of boron-based molecules with H2, CO, alkynes, alkenes and even with N2.

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Single and double activation of acetone by isolobal BN and BB triple bonds

Abstract: Polar and apolar boron-based triple bonds promote the single and double C–H activation of acetone following similar coordination-deprotonation mechanisms.

Cited by 39 publications

References 35 publications

Realization of an Al≡Al Triple Bond in the Gas‐Phase Na₃Al₂⁻ Cluster via Double Electronic Transmutation

Realization of an Al≡Al Triple Bond in the Gas‐Phase Na₃Al₂⁻ Cluster via Double Electronic Transmutation

Sequential Oxidation and C−H Bond Activation at a Gallium(I) Center

Metallomimetic Chemistry of Boron

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Single and double activation of acetone by isolobal BN and BB triple bonds

Abstract: Polar and apolar boron-based triple bonds promote the single and double C–H activation of acetone following similar coordination-deprotonation mechanisms.

Cited by 39 publications

References 35 publications

Realization of an Al≡Al Triple Bond in the Gas‐Phase Na3Al2− Cluster via Double Electronic Transmutation

Realization of an Al≡Al Triple Bond in the Gas‐Phase Na3Al2− Cluster via Double Electronic Transmutation

Sequential Oxidation and C−H Bond Activation at a Gallium(I) Center

Metallomimetic Chemistry of Boron

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Product

Resources

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Realization of an Al≡Al Triple Bond in the Gas‐Phase Na₃Al₂⁻ Cluster via Double Electronic Transmutation

Realization of an Al≡Al Triple Bond in the Gas‐Phase Na₃Al₂⁻ Cluster via Double Electronic Transmutation