Loading…
[(acridine)BCl2]+: A Borenium Cation That Is a Strong Boron- and Carbon-Based Lewis Acid
[(acridine)BCl2][AlCl4] was synthesized by halide abstraction from (acridine)BCl3 with AlCl3. The hydride ion affinity of the C9 position in [(acridine)BCl2]+ was calculated to be 14 kcal mol–1 greater than that at boron. [(acridine)BCl2][AlCl4] reacts with 1 equiv of acridine to form the strained b...
Saved in:
Published in: | Organometallics 2013-11, Vol.32 (22), p.6712-6717 |
---|---|
Main Authors: | , |
Format: | Article |
Language: | English |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
Summary: | [(acridine)BCl2][AlCl4] was synthesized by halide abstraction from (acridine)BCl3 with AlCl3. The hydride ion affinity of the C9 position in [(acridine)BCl2]+ was calculated to be 14 kcal mol–1 greater than that at boron. [(acridine)BCl2][AlCl4] reacts with 1 equiv of acridine to form the strained boronium cation [(acridine)2BCl2][AlCl4] and with P(mesityl)3 by photoinduced one-electron transfer to form the 9,9′-biacridane moiety by radical coupling. A stable frustrated Lewis pair (FLP) was formed on combining [(acridine)BCl2][AlCl4] and 2,4,6-tri-tert-butylpyridine (TBP), which heterolytically activated H2 at 100 °C. The ultimate location of the hydride from H2 activation was the C9 position of acridine and not boron. Carbon Lewis acid based reactivity also occurred when thieno[3,2-b]thiophene was added to the [(acridine)BCl2][AlCl4]/TBP FLP or to [(acridine)2BCl2][AlCl4], with arylation of acridine at C9 observed for both. |
---|---|
ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/om400463r |