Leitl, Julia and Jupp, Andrew R. and Habraken, Evi R. M. and Streitferdt, Verena and Coburger, Peter and Scott, Daniel J. and Gschwind, Ruth M. and Mueller, Christian and Slootweg, J. Chris and Wolf, Robert (2020) A Phosphinine-Derived 1-Phospha-7-Bora-Norbornadiene: Frustrated Lewis Pair Type Activation of Triple Bonds. CHEMISTRY-A EUROPEAN JOURNAL, 26 (35). pp. 7788-7800. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
Salt metathesis of 1-methyl-2,4,6-triphenylphosphacyclohexadienyl lithium and chlorobis(pentafluorophenyl)borane affords a 1-phospha-7-bora-norbornadiene derivative 2. The C equivalent to N triple bonds of nitriles insert into the P-B bond of 2 with concomitant C-B bond cleavage, whereas the C equivalent to C bonds of phenylacetylenes react with 2 to form lambda(4)-phosphabarrelenes. Even though 2 must formally be regarded as a classical Lewis adduct, the C equivalent to N and C equivalent to C activation processes observed (and the mild conditions under which they occur) are reminiscent of the reactivity of frustrated Lewis pairs. Indeed, NMR and computational studies give insight into the mechanism of the reactions and reveal the labile nature of the phosphorus-boron bond in 2, which is also suggested by detailed NMR spectroscopic studies on this compound. Nitrile insertion is thus preceded by ring opening of the bicycle of 2 through P-B bond splitting with a low energy barrier. By contrast, the reaction with alkynes involves formation of a reactive zwitterionic methylphosphininium borate intermediate, which readily undergoes alkyne 1,4-addition.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | X-RAY CRYSTAL; LAMBDA(4)-PHOSPHININE ANION; CATALYZED HYDROFORMYLATION; COVALENT RADII; REACTIVITY; COMPLEXES; 2,4,6-TRIPHENYLPHOSPHININE; LIGANDS; COORDINATION; REDUCTION; alkyne; frustrated Lewis pair; nitrile; norbornadiene; phosphinine |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf Chemistry and Pharmacy > Institut für Organische Chemie Chemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 23 Mar 2021 09:24 |
| Last Modified: | 23 Mar 2021 09:24 |
| URI: | https://pred.uni-regensburg.de/id/eprint/44514 |
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