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Issue 8, 2011
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Group 13 BN dehydrocoupling reagents, similar to transition metal catalysts but with unique reactivity

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Abstract

Reactions of the AlIII and GaIII bases Al(NiPr2)3 and E(NMe2)3 (E = Al, Ga) with the amine-boranes [iPr2NHBH3] and [tBuNH2BH3] give the amino-borane monomer [iPr2N = BH2] (4) and the borazine [tBuNBH]3 (5), respectively. This is similar to the results of dehydrocoupling previously seen with single-site RhI catalysts and appears to occur via intermediate group 13 hydrides, as shown by the isolation of the amido-alane [H2Al(μ-NiPr2)]2 (7) in the formation of 4 from Al(NiPr2)3. In general, the outcome of group 13 dehydrocoupling reactions show a marked dependence on the amine-borane used and on the nucleophilic and redox character of the group 13 pre-catalyst. The importance of these factors is seen in the formation of the unusual, delocalised amino-borane [B{(NHBH)N(SiMe3)Si(Me2)N(SiMe3)2}3] (10) in the non-catalytic reaction of [Ga{N(SiMe3)2}3] with [NH3BH3], in which coupling of B–N as well as Si–N bonds occurs along with the deposition of Ga metal.

Graphical abstract: Group 13 BN dehydrocoupling reagents, similar to transition metal catalysts but with unique reactivity

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Supplementary files

Article information


Submitted
16 Mar 2011
Accepted
28 Apr 2011
First published
02 Jun 2011

Chem. Sci., 2011,2, 1554-1559
Article type
Edge Article

Group 13 BN dehydrocoupling reagents, similar to transition metal catalysts but with unique reactivity

M. M. Hansmann, R. L. Melen and D. S. Wright, Chem. Sci., 2011, 2, 1554
DOI: 10.1039/C1SC00154J

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