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

Hansmann, Max M., Melen, Rebecca L. and Wright, Dominic S. 2011. Group 13 BN dehydrocoupling reagents, similar to transition metal catalysts but with unique reactivity. Chemical Science 2 (8) , pp. 1554-1559. 10.1039/c1sc00154j

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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.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: Royal Society of Chemistry
ISSN: 2041-6520
Date of Acceptance: 28 April 2011
Last Modified: 04 Jun 2017 06:49
URI: http://orca.cf.ac.uk/id/eprint/65050

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