A Journey from Benzoborirene to Benzoborole-Supported 1,2-Diimine and Antiaromatic Borolediide

Liu，Xiaocui1,2; Heinz，Myron3; Wang，Junyi2; Tan，Leibo4; Holthausen，Max C.3; Ye，Qing4

2023-12-18

10.1002/anie.202312608

Angewandte Chemie - International Edition   影响因子和分区

1433-7851

1521-3773

The reaction of benzoborirene with one equivalent of isocyanides leads to benzene-fused boretes bearing one imine function, while the reaction with two equivalents of isocyanide affords 2,3-dihydro-2,3-diiminoboroles with perfect regioselectivity. The isocyanide double insertion products represent a novel type of 1,2-diimine with a benzoborole backbone. The reduction chemistry of the benzoborole-supported 1,2-diimine was investigated. Single- and two-electron reduction allow for the isolation and full characterization of a radical anion and a dianion, respectively. In stark contrast to the ordinary boroles, which should turn aromatic by accepting two electrons, the antiaromatic character of the benzoborole backbone is highlighted upon reduction, thus presenting a rare example of antiaromatic borole dianion. Detailed quantum chemical calculations provide a rationale for the observed regioselectivity and the electronic structure of the reduced borole diimine species.

Antiaromaticity Borirene Borole Diimine Radical

SCI ; EI

英语

NI论文

其他

WOS:001096627300001

20234515022503

Cyanides ; Electronic structure ; Quantum chemistry

Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Inorganic Compounds:804.2

CHEMISTRY

2-s2.0-85175646012

Scopus

1.State Key Laboratory of Traditional Chinese Medicine Syndromes,The Second Affiliated Hospital of Guangzhou University of Chinese Medicine,Guangzhou,510000,China
2.Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China
3.Institute of Inorganic and Analytical Chemistry,Goethe-Universität,Frankfurt am Main,60438,Germany
4.Institute für Anorganische Chemie and Institute for Sustainable Chemistry & Catalysis with Boron,Julius-Maximilians-Universität Würzburg,Würzburg,97074,Germany

Liu，Xiaocui,Heinz，Myron,Wang，Junyi,et al. A Journey from Benzoborirene to Benzoborole-Supported 1,2-Diimine and Antiaromatic Borolediide[J]. Angewandte Chemie - International Edition,2023,62(51).

Liu，Xiaocui,Heinz，Myron,Wang，Junyi,Tan，Leibo,Holthausen，Max C.,&Ye，Qing.(2023).A Journey from Benzoborirene to Benzoborole-Supported 1,2-Diimine and Antiaromatic Borolediide.Angewandte Chemie - International Edition,62(51).

Liu，Xiaocui,et al."A Journey from Benzoborirene to Benzoborole-Supported 1,2-Diimine and Antiaromatic Borolediide".Angewandte Chemie - International Edition 62.51(2023).