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The Reactivity of Isomeric Nitrenium Lewis Acids with Phosphines, Carbenes, and Phosphide

Alkylation of spiro[fluorene‐9,3’‐indazole] at N(1) and N(2) with tBuCl affords the nitrenium cations [C(6)H(4)N(2)(tBu)C(C(12)H(8))][BF(4)], 1 and 2, respectively. Compound 1 converts to 2 over the temperature range 303–323 K with a free energy barrier of 28±5 kcal mol(−1). Reaction of 1 with PMe(3...

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Autores principales: Zhu, Diya, Qu, Zheng‐Wang, Zhou, Jiliang, Stephan, Douglas W.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7898612/
https://www.ncbi.nlm.nih.gov/pubmed/33137240
http://dx.doi.org/10.1002/chem.202004798
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author Zhu, Diya
Qu, Zheng‐Wang
Zhou, Jiliang
Stephan, Douglas W.
author_facet Zhu, Diya
Qu, Zheng‐Wang
Zhou, Jiliang
Stephan, Douglas W.
author_sort Zhu, Diya
collection PubMed
description Alkylation of spiro[fluorene‐9,3’‐indazole] at N(1) and N(2) with tBuCl affords the nitrenium cations [C(6)H(4)N(2)(tBu)C(C(12)H(8))][BF(4)], 1 and 2, respectively. Compound 1 converts to 2 over the temperature range 303–323 K with a free energy barrier of 28±5 kcal mol(−1). Reaction of 1 with PMe(3) afforded the N‐bound phosphine adduct [C(6)H(4)N(tBu)N(PMe(3))C(C(12)H(8))]BF(4)] 3. However, phosphines attack 2 at the para‐carbon atom of the aryl group with concurrent cleavage of N(2)−C(1) bond and proton migration to C(1) affording [(R(3)P)C(6)H(3)NN(tBu)CH(C(12)H(8))][BF(4)] (R=Me 4, nBu 5). Analogous reactions of 1 and 2 with the carbene SIMes prompt attack at the para‐carbon with concurrent loss of H(.) affording the radical cation salts [(SIMes)C(6)H(3)N(tBu)NC(C(12)H(8))(.)][BF(4)] 6 and [(SIMes)C(6)H(3)NN(tBu)C(C(12)H(8))(.)][BF(4)] 7, whereas reaction of 2 with BAC gives the Lewis acid‐base adduct, [C(6)H(4)N(BAC)N(tBu)C(C(12)H(8))][BF(4)] 8. Finally, reactions of 1 and 2 with KPPh(2) result in electron transfer affording (PPh(2))(2) and the persistent radicals C(6)H(4)N(tBu)NC(C(12)H(8))(.) and C(6)H(4)NN(tBu)C(C(12)H(8))(.). The detailed reaction mechanisms are also explored by extensive DFT calculations.
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spelling pubmed-78986122021-03-03 The Reactivity of Isomeric Nitrenium Lewis Acids with Phosphines, Carbenes, and Phosphide Zhu, Diya Qu, Zheng‐Wang Zhou, Jiliang Stephan, Douglas W. Chemistry Full Papers Alkylation of spiro[fluorene‐9,3’‐indazole] at N(1) and N(2) with tBuCl affords the nitrenium cations [C(6)H(4)N(2)(tBu)C(C(12)H(8))][BF(4)], 1 and 2, respectively. Compound 1 converts to 2 over the temperature range 303–323 K with a free energy barrier of 28±5 kcal mol(−1). Reaction of 1 with PMe(3) afforded the N‐bound phosphine adduct [C(6)H(4)N(tBu)N(PMe(3))C(C(12)H(8))]BF(4)] 3. However, phosphines attack 2 at the para‐carbon atom of the aryl group with concurrent cleavage of N(2)−C(1) bond and proton migration to C(1) affording [(R(3)P)C(6)H(3)NN(tBu)CH(C(12)H(8))][BF(4)] (R=Me 4, nBu 5). Analogous reactions of 1 and 2 with the carbene SIMes prompt attack at the para‐carbon with concurrent loss of H(.) affording the radical cation salts [(SIMes)C(6)H(3)N(tBu)NC(C(12)H(8))(.)][BF(4)] 6 and [(SIMes)C(6)H(3)NN(tBu)C(C(12)H(8))(.)][BF(4)] 7, whereas reaction of 2 with BAC gives the Lewis acid‐base adduct, [C(6)H(4)N(BAC)N(tBu)C(C(12)H(8))][BF(4)] 8. Finally, reactions of 1 and 2 with KPPh(2) result in electron transfer affording (PPh(2))(2) and the persistent radicals C(6)H(4)N(tBu)NC(C(12)H(8))(.) and C(6)H(4)NN(tBu)C(C(12)H(8))(.). The detailed reaction mechanisms are also explored by extensive DFT calculations. John Wiley and Sons Inc. 2021-01-14 2021-02-05 /pmc/articles/PMC7898612/ /pubmed/33137240 http://dx.doi.org/10.1002/chem.202004798 Text en © 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Full Papers
Zhu, Diya
Qu, Zheng‐Wang
Zhou, Jiliang
Stephan, Douglas W.
The Reactivity of Isomeric Nitrenium Lewis Acids with Phosphines, Carbenes, and Phosphide
title The Reactivity of Isomeric Nitrenium Lewis Acids with Phosphines, Carbenes, and Phosphide
title_full The Reactivity of Isomeric Nitrenium Lewis Acids with Phosphines, Carbenes, and Phosphide
title_fullStr The Reactivity of Isomeric Nitrenium Lewis Acids with Phosphines, Carbenes, and Phosphide
title_full_unstemmed The Reactivity of Isomeric Nitrenium Lewis Acids with Phosphines, Carbenes, and Phosphide
title_short The Reactivity of Isomeric Nitrenium Lewis Acids with Phosphines, Carbenes, and Phosphide
title_sort reactivity of isomeric nitrenium lewis acids with phosphines, carbenes, and phosphide
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7898612/
https://www.ncbi.nlm.nih.gov/pubmed/33137240
http://dx.doi.org/10.1002/chem.202004798
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