E.-M. Rummel, M. Elsayed Moussa, M. Parzefall, E. Peresypkina, C. Riesinger, A. Y. Timoshkin, G. Balázs, P. Mastrorilli, S. Todisco and Manfred Scheer
{"title":"Synthesis, oxidation and unusual coordination chemistry of the diphosphete complex [(Cp′′′Co)2(μ,η4:4-(CH3CP)2)]†","authors":"E.-M. Rummel, M. Elsayed Moussa, M. Parzefall, E. Peresypkina, C. Riesinger, A. Y. Timoshkin, G. Balázs, P. Mastrorilli, S. Todisco and Manfred Scheer","doi":"10.1039/D4QI02643H","DOIUrl":null,"url":null,"abstract":"<p >Notwithstanding four decades of active research, very rare examples of diphosphabutadiene complexes arising from dimerisation of the phosphaalkyne CH<small><sub>3</sub></small>–C<img>P have been reported. Herein, we show that methyl phosphaalkyne dimerises in the coordination sphere of Cp′′′Co fragments to yield the unprecedented diphosphete complex [Cp′′′Co(η<small><sup>4</sup></small>-P<small><sub>2</sub></small>C<small><sub>2</sub></small>Me<small><sub>2</sub></small>)] (<strong>1</strong>) and the triple-decker complex [{Cp′′′Co}<small><sub>2</sub></small>(μ,η<small><sup>4</sup></small>:η<small><sup>4</sup></small>-P<small><sub>2</sub></small>C<small><sub>2</sub></small>Me<small><sub>2</sub></small>)] (<strong>2</strong>). Compound <strong>2</strong> can be oxidised with Ag[Al{OC(CF<small><sub>3</sub></small>)<small><sub>3</sub></small>}<small><sub>4</sub></small>] (Ag[TEF]) to give [{Cp′′′Co}<small><sub>2</sub></small>(μ,η<small><sup>4</sup></small>:η<small><sup>4</sup></small>-P<small><sub>2</sub></small>C<small><sub>2</sub></small>Me<small><sub>2</sub></small>)][TEF] (<strong>3</strong>). Additionally, it shows an unusual coordination behaviour towards copper halides and [W(CO)<small><sub>4</sub></small>(nbd)] (nbd = norbornadiene). Its reaction with CuCl leads to the formation of the 1D polymer [{Cp′′′Co}<small><sub>2</sub></small>(μ,η<small><sup>4</sup></small>:η<small><sup>2</sup></small>:η<small><sup>1</sup></small>:η<small><sup>1</sup></small>-P<small><sub>2</sub></small>C<small><sub>2</sub></small>Me<small><sub>2</sub></small>){Cu(μ-Cl)}<small><sub>2</sub></small>]<small><sub><em>n</em></sub></small> (<strong>6</strong>) while its reaction with CuBr, CuI and [W(CO)<small><sub>4</sub></small>(nbd)] results in the metallacyclic compounds [(Cp′′′Co){μ<small><sub>3</sub></small>,η<small><sup>4</sup></small>:η<small><sup>1</sup></small>:η<small><sup>1</sup></small>-P<small><sub>2</sub></small>C<small><sub>2</sub></small>Me<small><sub>2</sub></small>}(CH<small><sub>3</sub></small>CN){Cu(μ-X)}<small><sub>2</sub></small>]<small><sub>2</sub></small> (X = Br (<strong>7a</strong>), I (<strong>7b</strong>)) and [Cp′′′Co{μ<small><sub>3</sub></small>,η<small><sup>4</sup></small>:η<small><sup>1</sup></small>:η<small><sup>1</sup></small>-P<small><sub>2</sub></small>C<small><sub>2</sub></small>Me<small><sub>2</sub></small>}{W(CO)<small><sub>4</sub></small>}]<small><sub>3</sub></small> (<strong>8</strong>). In <strong>6</strong>, an isomerisation of the diphosphete ring to a diphosphacyclopentadienyl ring occurs. In <strong>7</strong> and <strong>8</strong>, the loss of Cp′′′Co moieties from the former compound <strong>2</strong> is observed. The formation of 1,3-diphosphete rings in <strong>1</strong> and <strong>2</strong> instead of the more thermodynamically favoured 1,2-diphosphete rings are explained by DFT computations.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 3","pages":" 967-974"},"PeriodicalIF":6.1000,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/qi/d4qi02643h","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Notwithstanding four decades of active research, very rare examples of diphosphabutadiene complexes arising from dimerisation of the phosphaalkyne CH3–CP have been reported. Herein, we show that methyl phosphaalkyne dimerises in the coordination sphere of Cp′′′Co fragments to yield the unprecedented diphosphete complex [Cp′′′Co(η4-P2C2Me2)] (1) and the triple-decker complex [{Cp′′′Co}2(μ,η4:η4-P2C2Me2)] (2). Compound 2 can be oxidised with Ag[Al{OC(CF3)3}4] (Ag[TEF]) to give [{Cp′′′Co}2(μ,η4:η4-P2C2Me2)][TEF] (3). Additionally, it shows an unusual coordination behaviour towards copper halides and [W(CO)4(nbd)] (nbd = norbornadiene). Its reaction with CuCl leads to the formation of the 1D polymer [{Cp′′′Co}2(μ,η4:η2:η1:η1-P2C2Me2){Cu(μ-Cl)}2]n (6) while its reaction with CuBr, CuI and [W(CO)4(nbd)] results in the metallacyclic compounds [(Cp′′′Co){μ3,η4:η1:η1-P2C2Me2}(CH3CN){Cu(μ-X)}2]2 (X = Br (7a), I (7b)) and [Cp′′′Co{μ3,η4:η1:η1-P2C2Me2}{W(CO)4}]3 (8). In 6, an isomerisation of the diphosphete ring to a diphosphacyclopentadienyl ring occurs. In 7 and 8, the loss of Cp′′′Co moieties from the former compound 2 is observed. The formation of 1,3-diphosphete rings in 1 and 2 instead of the more thermodynamically favoured 1,2-diphosphete rings are explained by DFT computations.