Isolation of Stable Borepin Radicals and Anions

Hollister, Kimberly; Yang, Wenlong; Mondol, Ranajit; Krantz, Kelsie E.; Molino, Andrew; Kaur, Aishvaryadeep; Dickie, Diane A.; Frenking, Gernot; Pan, Sudip; Wilson, David J.; Gilliard, Robert J.

doi:10.1002/ange.202202516

Cited by 6 publications

(2 citation statements)

References 78 publications

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“…2b). The obtained relatively weak hyperfine coupling to boron is typical for CAAC-stabilized neutral boron radicals [43][44][45][46][47] . Crystalline 2 • obtained from slow evaporation of a pentane solution of 2 • in a glovebox was analyzed with single crystal X-ray diffraction.…”

Section: Synthesis Of Di-coordinate Boron Radical Cationmentioning

confidence: 73%

“…X-ray diffraction analysis on a single crystal of [6][B(C 6 F 5 ) 4 ] obtained from a DCM/pentane solution at -30 °C corroborated the formation of a tri-coordinate boron radical cation, a much less explored boron radical class (Fig. 4b) [46][47][48][49][50] . Compared to the reported homoleptic analogs, the base coordination reaction of [3] +• represents a straightforward synthetic method to boron radical cations with a heterolepic coordination environment 51,52 .…”

Section: Reactions Of [3] +•mentioning

confidence: 85%

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A linear Di-coordinate boron radical cation

Lin

Liu

et al. 2022

Nat Commun

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The pursuit of di-coordinate boron radical has been continued for more than a half century, and their stabilization and structural characterization remains a challenge. Here we report the isolation and structural characterization of a linear di-coordinate boron radical cation, achieved by stabilizing the two reactive atomic orbitals of the central boron atom by two orthogonal π-donating and π-accepting functionalities. The electron deficient radical cation undergoes facile one-electron reduction to borylene and binds Lewis base to give heteroleptic tri-coordinate boron radical cation. The co-existence of half-filled and empty p orbitals at boron also allows the CO-regulated electron transfer to be explored. As the introduction of CO promotes the electron transfer from a tri-coordinate neutral boron radical to a boron radical cation, the removal of CO under vacuum furnishes the reverse electron transfer from borylene to yield a solution consisting of two boron radicals.

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Section: Synthesis Of Di-coordinate Boron Radical Cationmentioning

confidence: 73%

Section: Reactions Of [3] +•mentioning

confidence: 85%

A linear Di-coordinate boron radical cation

Lin

Liu

et al. 2022

Nat Commun

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Gauging Radical Stabilization with Carbenes

et al. 2022

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Carbenes, including N‐heterocyclic carbene (NHC) ligands, are used extensively to stabilize open‐shell transition metal complexes and organic radicals. Yet, it remains unknown, which carbene stabilizes a radical well and, thus, how to design radical‐stabilizing C‐donor ligands. With the large variety of C‐donor ligands experimentally investigated and their electronic properties established, we report herein their radical‐stabilizing effect. We show that radical stabilization can be understood by a captodative frontier orbital description involving π‐donation to‐ and π‐donation from the carbenes. This picture sheds a new perspective on NHC chemistry, where π‐donor effects usually are assumed to be negligible. Further, it allows for the intuitive prediction of the thermodynamic stability of covalent radicals of main group‐ and transition metal carbene complexes, and the quantification of redox non‐innocence.

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Gauging Radical Stabilization with Carbenes

et al. 2022

View full text Add to dashboard Cite

Carbenes, including N-heterocyclic carbene (NHC) ligands, are used extensively to stabilize openshell transition metal complexes and organic radicals. Yet, it remains unknown, which carbene stabilizes a radical well and, thus, how to design radical-stabilizing C-donor ligands. With the large variety of C-donor ligands experimentally investigated and their electronic properties established, we report herein their radicalstabilizing effect. We show that radical stabilization can be understood by a captodative frontier orbital description involving π-donation to-and π-donation from the carbenes. This picture sheds a new perspective on NHC chemistry, where π-donor effects usually are assumed to be negligible. Further, it allows for the intuitive prediction of the thermodynamic stability of covalent radicals of main group-and transition metal carbene complexes, and the quantification of redox non-innocence.

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Isolation of Stable Borepin Radicals and Anions

Cited by 6 publications

References 78 publications

A linear Di-coordinate boron radical cation

A linear Di-coordinate boron radical cation

Gauging Radical Stabilization with Carbenes

Gauging Radical Stabilization with Carbenes

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