An unsymmetrical, cyclic diborene based on a chelating CAAC ligand and its small-molecule activation and rearrangement chemistry
Please always quote using this URN: urn:nbn:de:bvb:20-opus-256576
- A one-pot synthesis of a CAAC-stabilized, unsymmetrical, cyclic diborene was achieved via consecutive two-electron reduction steps from an adduct of CAAC and B\(_2\)Br\(_4\)(SMe\(_2\))\(_2\). Theoretical studies revealed that this diborene has a considerably smaller HOMO–LUMO gap than those of reported NHC- and phosphine-supported diborenes. Complexation of the diborene with [AuCl(PCy\(_3\))] afforded two diborene–Au\(^I\) π complexes, while reaction with DurBH\(_2\), P\(_4\) and a terminal acetylene led to the cleavage of B−H, P−P, and C−CA one-pot synthesis of a CAAC-stabilized, unsymmetrical, cyclic diborene was achieved via consecutive two-electron reduction steps from an adduct of CAAC and B\(_2\)Br\(_4\)(SMe\(_2\))\(_2\). Theoretical studies revealed that this diborene has a considerably smaller HOMO–LUMO gap than those of reported NHC- and phosphine-supported diborenes. Complexation of the diborene with [AuCl(PCy\(_3\))] afforded two diborene–Au\(^I\) π complexes, while reaction with DurBH\(_2\), P\(_4\) and a terminal acetylene led to the cleavage of B−H, P−P, and C−C π bonds, respectively. Thermal rearrangement of the diborene gave an electron-rich cyclic alkylideneborane, which readily coordinated to Ag\(^I\) via its B=C double bond.…
Author: | Wei LuORCiD, Arumugam JayaramanORCiD, Felipe FantuzziORCiD, Rian D. DewhurstORCiD, Marcel HärterichORCiD, Maximilian Dietz, Stephan Hagspiel, Ivo KrummenbacherORCiD, Kai Hammond, Jingjing Cui, Holger BraunschweigORCiD |
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URN: | urn:nbn:de:bvb:20-opus-256576 |
Document Type: | Journal article |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Language: | English |
Parent Title (English): | Angewandte Chemie International Edition |
Year of Completion: | 2022 |
Volume: | 61 |
Issue: | 3 |
Article Number: | e202113947 |
Source: | Angewandte Chemie International Edition (2022) 61:3, e202113947. DOI: 10.1002/anie.202113947 |
DOI: | https://doi.org/10.1002/anie.202113947 |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie |
Tag: | alkylideneborane; carbene; diborene; inorganic chemistry; thermal rearrangement |
Release Date: | 2022/02/25 |
EU-Project number / Contract (GA) number: | 669054 |
OpenAIRE: | OpenAIRE |
Licence (German): | CC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International |