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Attempts toward a Silyl-Stabilized Dicoordinate Borylene: Insertion of Carbon Dioxide into the B-Si Bond
Kasperi M Salonen1, J Mikko Rautiainen1, Aaron Mailman1
1Department of Chemistry, NanoScience Center, University of Jyväskylä, P.O. Box 35, Jyväskylä FI-40014, Finland.
Abstract:
One-electron reduction of the carbene-stabilized borane (Me2-cAAC)B(Cl)2Si(SiMe3)3, 1, with potassium naphthalenide gave the radical (Me2-cAAC)B(Cl)Si(SiMe3)3, 2. A subsequent one-electron reduction of 2 yielded the dicoordinate borylene (Me2-cAAC)BSi(SiMe3)3, 3, which rapidly underwent intramolecular C-H activation to give cyclo-(Me2-cAAC)B(H)Si(SiMe3)3, 4, irrespective of the employed reaction conditions. Compound 3 could be stabilized as the carbonyl complex (Me2-cAAC)B(CO)Si(SiMe3)3, 5, that gave 4 upon irradiation with a UV light under a CO2 atmosphere. In contrast, the two-electron reduction of 1 under an atmosphere of CO2 yielded a mixture of products of which (Me2-cAAC)B(Cl)(H)C(O)OSi(SiMe3)3, 6, could be separated and structurally characterized. Compound 6 is a rare example of CO2 insertion into a B-E (E = heavier main group element) bond in which boron functions as a nucleophile, thereby mimicking transition metal-mediated carboxylation. The mechanism for the formation of 6 from the purported boryl anion intermediate [(Me2-cAAC)B(Cl)Si(SiMe3)3]-, 2 -, was analyzed computationally.
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