Transient Phosphenium and Arsenium Ions Versus Stable Stibenium and Bismuthenium Ions

Overview

Journal Chemistry

Specialty Chemistry

Date 2019 Aug 13

PMID 31404472

Citations 5

Authors

Marian Olaru

Daniel Duvinage

Enno Lork

Stefan Mebs

Jens Beckmann

Affiliations

Soon will be listed here.

Abstract

Fluoride abstraction from bis-m-terphenylelement fluorides (2,6-Mes C H ) EF (E=P, As) generated the highly reactive phosphenium ion [(2,6-Mes C H ) P] and the arsenium ion [(2,6-Mes C H ) As] , which immediately underwent intramolecular electrophilic substitution and formation of an 1,2,4-trimethyl-6-mesityl-5-m-terphenyl-benzo[b]phospholium ion and an 1,2,4-trimethyl-6-mesityl-5-m-terphenyl-benzo[b]arsolium ion, respectively. The formation of the latter involved a methyl group migration from the ortho-position of a flanking mesityl group to the meta-position. This reactivity of [(2,6-Mes C H ) E] (E=P, As) is in sharp contrast to the related stibenium ion [(2,6-Mes C H ) Sb] and bismuthenium ion [(2,6-Mes C H ) Bi] , which have been recently isolated and fully characterized (Angew. Chem. Int. Ed. 2018, 57, 10080-10084). On the basis of DFT calculations, a mechanism for the rearrangement of the phosphenium and arsenium ions into the phospholium and arsolium ions is proposed, which is not feasible for the stibenium and bismuthenium ions.

Citing Articles

Cationic Carbene Analogues: Donor-Free Phosphenium and Arsenium Ions.

Olaru M, Mebs S, Beckmann J Angew Chem Int Ed Engl. 2021; 60(35):19133-19138.

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Isolation of an Antiaromatic 9-Hydroxy Fluorenyl Cation.

Duvinage D, Mebs S, Beckmann J Chemistry. 2021; 27(31):8105-8109.

PMID: 33835609 PMC: 8252458. DOI: 10.1002/chem.202100786.

Intramolecular Reaction of Transient Phosphenium and Arsenium Ions Giving Rise to Isolable 9-Phospha- and 9-Arsena-Fluorenium Ions.

Olaru M, Duvinage D, Nass Y, Malaspina L, Mebs S, Beckmann J Angew Chem Int Ed Engl. 2020; 59(34):14414-14417.

PMID: 32460394 PMC: 7496934. DOI: 10.1002/anie.202006728.

The Bis(ferrocenyl)phosphenium Ion Revisited.

Olaru M, Mischin A, Malaspina L, Mebs S, Beckmann J Angew Chem Int Ed Engl. 2019; 59(4):1581-1584.

PMID: 31751492 PMC: 7003730. DOI: 10.1002/anie.201913081.

Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions.

Olaru M, Duvinage D, Lork E, Mebs S, Beckmann J Chemistry. 2019; 25(65):14758-14761.

PMID: 31404472 PMC: 6900177. DOI: 10.1002/chem.201902520.

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