New Insights in Frustrated Lewis Pair Chemistry with Azides
| Authors |
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| Publication date | 17-10-2019 |
| Journal | Chemistry-A European Journal |
| Volume | Issue number | 25 | 58 |
| Pages (from-to) | 13299-13308 |
| Number of pages | 10 |
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| Abstract |
The geminal frustrated Lewis pair (FLP) tBu2PCH2BPh2 (1) reacts with phenyl‐, mesityl‐, and tert‐butyl azide affording, respectively, six, five, and four‐membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six‐membered ring structure, which is thermally stable with an N‐phenyl group, but rearranges when sterically more encumbered Mes−N3 and tBu−N3 are used. The reaction of 1 with Me3Si−N3 is believed to follow the same course, yet subsequent N2 elimination occurs to afford a four‐membered heterocycle (5), which can be considered as a formal FLP‐trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.
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| Document type | Article |
| Note | With supplementary file |
| Language | English |
| Related dataset | CCDC 1896718: Experimental Crystal Structure Determination CCDC 1896719: Experimental Crystal Structure Determination CCDC 1896720: Experimental Crystal Structure Determination CCDC 1896723: Experimental Crystal Structure Determination CCDC 1896721: Experimental Crystal Structure Determination CCDC 1896722: Experimental Crystal Structure Determination |
| Published at | https://doi.org/10.1002/chem.201902710 |
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New Insights in Frustrated Lewis Pair Chemistry with Azides
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