TY - JOUR
T1 - Synthesis and Reactivity of Cationic Boron Complexes Distorted by Pyridine-based Pincer Ligands
T2 - Isolation of a Photochemical Hofmann–Martius-type Intermediate
AU - Janes, Trevor
AU - Diskin-Posner, Yael
AU - Milstein, David
PY - 2020/3/16
Y1 - 2020/3/16
N2 - A family of cationic boron complexes was synthesized, using a dianilidopyridine pincer ligand, which imposes in-plane distortion of the geometry at boron towards T-shaped. Reactivity of these cations toward hydride and base was investigated, and the utility of these cations as precursors to a variety of π-conjugated BN heterocycles was demonstrated. 300 nm irradiation of a deprotonated pincer boron complex triggered a C−N cleavage/C−C formation yielding a dearomatized boryl imine, which has a structure akin to the long-proposed intermediate in the photochemical Hofmann–Martius rearrangement. The photo-rearrangement triggers relief of the distortion imposed by the pincer ligand.
AB - A family of cationic boron complexes was synthesized, using a dianilidopyridine pincer ligand, which imposes in-plane distortion of the geometry at boron towards T-shaped. Reactivity of these cations toward hydride and base was investigated, and the utility of these cations as precursors to a variety of π-conjugated BN heterocycles was demonstrated. 300 nm irradiation of a deprotonated pincer boron complex triggered a C−N cleavage/C−C formation yielding a dearomatized boryl imine, which has a structure akin to the long-proposed intermediate in the photochemical Hofmann–Martius rearrangement. The photo-rearrangement triggers relief of the distortion imposed by the pincer ligand.
KW - BN heterocycles
KW - C−C bond formation
KW - Hofmann–Martius rearrangement
KW - boron cations
KW - pincer ligands
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U2 - 10.1002/anie.202000406
DO - 10.1002/anie.202000406
M3 - Article
C2 - 31967728
AN - SCOPUS:85078961824
VL - 59
SP - 4932
EP - 4936
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 12
ER -