Synthesis, oxidation and unusual coordination chemistry of the diphosphete complex [(Cp′′′Co)2(μ,η4:4-(CH3CP)2)]†

IF 6.1 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
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,η44-P2C2Me2)] (2). Compound 2 can be oxidised with Ag[Al{OC(CF3)3}4] (Ag[TEF]) to give [{Cp′′′Co}2(μ,η44-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,η4211-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){μ3411-P2C2Me2}(CH3CN){Cu(μ-X)}2]2 (X = Br (7a), I (7b)) and [Cp′′′Co{μ3411-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.

Abstract Image

二磷酸盐配合物[(Cp'' Co)2(μ,η4:4-((CH3) Cp)2)]的合成、氧化及异常配位化学研究
尽管经过40年的积极研究,由磷酸炔CH3-C≡P二聚化产生的二磷酸丁二烯配合物的例子非常罕见。在此,我们发现甲基磷烷在Cp'' Co片段的配位球中二聚生成了前所未有的二磷酸盐配合物[Cp'' Co(η - 4-P2C2Me2)](1)和三层配合物[{Cp'' Co}2(μ,η4:η4 P2C2Me2)](2)。化合物2可以与Ag[Al{OC(CF3)3}4] (Ag[TEF])氧化得到[{Cp'' Co}2(μ,η4:η4 P2C2Me2)][TEF](3)。此外,它与卤化铜和[W(Co)4(nbd)] (nbd =降冰片二烯)表现出不同寻常的配位行为。它与CuCl反应生成1D聚合物[{Cp'' Co}2(μ,η4:η2:η1 - p2c2me2){Cu(μ -Cl)}2]n(6),与cur、CuI和[W(Co) 4(nbd)]反应生成金属环化合物[(Cp'' Co){μ3,η4:η1 - p2c2me2}(CH3CN){Cu(μ-X)}2]2 (X = Br (7a), I (7b))和[Cp'' Co{μ3,η4:η1 - p2c2me2}{W(Co) 4}]3(8)。在6中,二磷酸盐环异构化成二磷环戊二烯基环。在7和8中,观察到前化合物2的Cp'' Co部分的损失。用DFT计算解释了在1和2中形成1,3-二磷酸盐环,而不是在热力学上更有利的1,2-二磷酸盐环。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
Inorganic Chemistry Frontiers
Inorganic Chemistry Frontiers CHEMISTRY, INORGANIC & NUCLEAR-
CiteScore
10.40
自引率
7.10%
发文量
587
审稿时长
1.2 months
期刊介绍: The international, high quality journal for interdisciplinary research between inorganic chemistry and related subjects
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信