Incorporation of Boron into Uranium Metallacycles: Synthesis,Structure, and Reactivity of Boron-Containing Uranacycles Derived from Bis(alkynyl)boranes |
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| Authors: | Dr Wangyang Ma Iskander Douair Prof?Dr Laurent Maron Prof?Dr Qing Ye |
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| Institution: | 1. Department of Chemistry, Southern University of Science and Technology, 518055 Shenzhen, China;2. LPCNO, CNRS & INSA, Université Paul Sabatier, Toulouse, France |
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| Abstract: | The reaction of uranacyclopropene complex (C5Me5)2Uη2-1,2-C2(SiMe3)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 (Me3Si)2NB(C≡CPh)2 afforded an unexpected uranaborabicyclo2.2.0] 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-iPr2-C6H3) and isocyanate tBuNCO afforded the novel uranaborabicyclo3.2.0] complexes. All new complexes have been structurally characterized. DFT calculations were performed to provide more insights into the electronic structures and the reaction mechanism. |
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| Keywords: | bis(alkynyl)borane boracycle boron-centered ligand uranacycle uranium |
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