Post‐assembly reaction of a dynamic covalent iminoboronate system following addition of Cp2Co resulted in the formation of a series of new reductively coupled dianionic dimers via C−C bond formation. The dimers formed as a mixture of BN‐containing isomeric products: diastereomers rac 5 and meso 5, with coupled five‐membered rings, and enantiomeric rac 6, with a fused six‐membered ring bicyclic system from C−C bond formation and rearrangement of the B−N bonds. Each isomer was identified using 1H NMR spectroscopy in combination with single crystal X‐ray structure determination. Interestingly, interconversion between the coupled five‐membered rings (rac 5) and fused bicyclic systems (rac 6) was found to occur through an unprecedented breaking and reforming of the B−N covalent bond. Further, the coupled products could be converted quantitatively back to their iminoboronate precursors with addition of the electron abstractor Ph3C+.

Protocols for the synthesis of the bulky polyfluorinated triarylboranes 2,6‐(C6F5)2C6F3B(C6F5)2 (1), 2,6‐(C6F5)2C6F3B[3,5‐(CF3)2C6H3] (2), 2,4,6‐(C6F5)3C6H2B(C6F5)2 (3), 2,4,6‐(C6F5)3C6H2B[3,5‐(CF3)2C6H3] (4) were developed. All boranes are water tolerant and according to the Gutmann‐Beckett method, 1–3 display Lewis acidities larger than that of the prominent B(C6F5)3.

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Intermolecular interactions between fluorine atoms, analogous to halogen bonding, are able to drive the solid-state arrangement of molecules.

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