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Incorporation of Boron into Uranium Metallacycles: Synthesis, Structure, and Reactivity of Boron‐Containing Uranacycles Derived from Bis(alkynyl)boranes
Author(s) -
Ma Wangyang,
Douair Iskander,
Maron Laurent,
Ye Qing
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202003611
Subject(s) - borane , boranes , chemistry , isocyanide , reactivity (psychology) , boron , medicinal chemistry , aryl , stereochemistry , organic chemistry , catalysis , medicine , alkyl , alternative medicine , pathology
The reaction of uranacyclopropene complex (C 5 Me 5 ) 2 U[η 2 ‐1,2‐C 2 (SiMe 3 ) 2 ] with B‐aryl bis(alkynyl)borane PhB(C≡ CPh ) 2 led to the first six‐membered uranium metallaboracycle, while the reaction with B‐amino bis(alkynyl)borane (Me 3 Si) 2 NB(C≡ CPh ) 2 afforded an unexpected uranaborabicyclo[2.2.0] complex via [2+2] cycloaddition. The reaction with CuCl revealed the non‐innocent property of the rearranged bis(alkynyl)boron species towards oxidant. The reactions with isocyanide DippNC: (Dipp=2,6‐ i Pr 2 ‐C 6 H 3 ) and isocyanate t BuNCO afforded the novel uranaborabicyclo[3.2.0] complexes. All new complexes have been structurally characterized. DFT calculations were performed to provide more insights into the electronic structures and the reaction mechanism.