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Direct Interconversion between Bis(borylenes) and Diborenes
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DOI：10.1021/jacs.5c17540.png)
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Abstract
En 中文
Over the past two decades, the chemistry of borylenes and their formal dimer, diborenes, has witnessed remarkable advances. However, direct evidence for a Wanzlick-type equilibrium between borylenes and diborenes has remained elusive. Here, we report CAAC-stabilized (CAAC = cyclic (alkyl)(amino)carbene) mono- and disubstituted ferrocene-based borylene systems. The monosubstituted ferrocene-based borylene undergoes intramolecular C–H, CO, and H2 activation, with the C–H activation products existing in equilibrium. Most notably, the disubstituted ferrocene-based bis(borylene) undergoes direct coupling to form a diborene featuring a unique delocalized four-center–two-electron (4c–2e) π bond. Remarkably, this diborene reversibly dissociates back into the bis(borylene), which can be trapped with CO or via intramolecular C–H activation. The electronic and rotational flexibility of the ferrocene scaffold plays a pivotal role in facilitating the reversible coupling and decoupling between these bis(borylene) and diborene species. Furthermore, the ferrocenyl diborene species exhibits distinctive photophysical properties, redox behavior and reactivities.
Journal
IF:
15.6
Papers:
20.0W
Citations:
60.2W