{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"omics_type":["Unknown"],"volume":["25(65)"],"submitter":["Olaru M"],"funding":["Deutsche Forschungsgemeinschaft"],"pubmed_abstract":["Fluoride abstraction from bis-m-terphenylelement fluorides (2,6-Mes<sub>2</sub> C<sub>6</sub> H<sub>3</sub> )<sub>2</sub> EF (E=P, As) generated the highly reactive phosphenium ion [(2,6-Mes<sub>2</sub> C<sub>6</sub> H<sub>3</sub> )<sub>2</sub> P]<sup>+</sup> and the arsenium ion [(2,6-Mes<sub>2</sub> C<sub>6</sub> H<sub>3</sub> )<sub>2</sub> As]<sup>+</sup> , 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<sub>2</sub> C<sub>6</sub> H<sub>3</sub> )<sub>2</sub> E]<sup>+</sup> (E=P, As) is in sharp contrast to the related stibenium ion [(2,6-Mes<sub>2</sub> C<sub>6</sub> H<sub>3</sub> )<sub>2</sub> Sb]<sup>+</sup> and bismuthenium ion [(2,6-Mes<sub>2</sub> C<sub>6</sub> H<sub>3</sub> )<sub>2</sub> Bi]<sup>+</sup> , 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."],"journal":["Chemistry (Weinheim an der Bergstrasse, Germany)"],"pagination":["14758-14761"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC6900177"],"repository":["biostudies-literature"],"pubmed_title":["Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions."],"pmcid":["PMC6900177"],"pubmed_authors":["Olaru M","Lork E","Beckmann J","Duvinage D","Mebs S"],"additional_accession":[]},"is_claimable":false,"name":"Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions.","description":"Fluoride abstraction from bis-m-terphenylelement fluorides (2,6-Mes<sub>2</sub> C<sub>6</sub> H<sub>3</sub> )<sub>2</sub> EF (E=P, As) generated the highly reactive phosphenium ion [(2,6-Mes<sub>2</sub> C<sub>6</sub> H<sub>3</sub> )<sub>2</sub> P]<sup>+</sup> and the arsenium ion [(2,6-Mes<sub>2</sub> C<sub>6</sub> H<sub>3</sub> )<sub>2</sub> As]<sup>+</sup> , 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<sub>2</sub> C<sub>6</sub> H<sub>3</sub> )<sub>2</sub> E]<sup>+</sup> (E=P, As) is in sharp contrast to the related stibenium ion [(2,6-Mes<sub>2</sub> C<sub>6</sub> H<sub>3</sub> )<sub>2</sub> Sb]<sup>+</sup> and bismuthenium ion [(2,6-Mes<sub>2</sub> C<sub>6</sub> H<sub>3</sub> )<sub>2</sub> Bi]<sup>+</sup> , 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.","dates":{"release":"2019-01-01T00:00:00Z","publication":"2019 Nov","modification":"2021-02-20T18:16:08Z","creation":"2020-05-21T23:33:19Z"},"accession":"S-EPMC6900177","cross_references":{"pubmed":["31404472"],"doi":["10.1002/chem.201902520"]}}