Linkun Miao, Amir Yeganeh-Salman, Jason Yeung and Douglas W. Stephan
{"title":"Synthesis and N–C bond cleavage reactions for cyclic phosphazenium dications†","authors":"Linkun Miao, Amir Yeganeh-Salman, Jason Yeung and Douglas W. Stephan","doi":"10.1039/D4DT02990A","DOIUrl":null,"url":null,"abstract":"<p >Phosphazenium cations were first characterized 60 years ago and yet little is known of their reactivity. The bidentate phosphonium dicationic salts [(C<small><sub>6</sub></small>H<small><sub>4</sub></small>)(PPh<small><sub>2</sub></small>F)<small><sub>2</sub></small>][B(C<small><sub>6</sub></small>F<small><sub>5</sub></small>)<small><sub>4</sub></small>]<small><sub>2</sub></small><strong>2</strong> and [(C<small><sub>6</sub></small>H<small><sub>4</sub></small>)(PPh<small><sub>2</sub></small>Cl)<small><sub>2</sub></small>][Cl]<small><sub>2</sub></small><strong>3</strong> were prepared. Reaction of <strong>2</strong> with (Me<small><sub>3</sub></small>Si)<small><sub>2</sub></small>NMe gave the phosphazenium dication [(C<small><sub>6</sub></small>H<small><sub>4</sub></small>)(PPh<small><sub>2</sub></small>)<small><sub>2</sub></small>(μ-NMe)][B(C<small><sub>6</sub></small>F<small><sub>5</sub></small>)<small><sub>4</sub></small>]<small><sub>2</sub></small><strong>4</strong>, while reaction of <strong>3</strong> with two equivalents of Me<small><sub>2</sub></small>N(SiMe<small><sub>3</sub></small>) gave the related dication [(C<small><sub>6</sub></small>H<small><sub>4</sub></small>)(PPh<small><sub>2</sub></small>NMe<small><sub>2</sub></small>)<small><sub>2</sub></small>][Cl]<small><sub>2</sub></small><strong>5</strong>. Compound <strong>3</strong> also reacted with (Me<small><sub>3</sub></small>Si)<small><sub>2</sub></small>NH affording the monocationic salt [(C<small><sub>6</sub></small>H<small><sub>4</sub></small>)(PPh<small><sub>2</sub></small>)<small><sub>2</sub></small>(μ-N)]Cl <strong>6</strong>, with the liberation of HCl. Interestingly <strong>4</strong> reacted with [nBu<small><sub>4</sub></small>N]Cl generating the related salt [(C<small><sub>6</sub></small>H<small><sub>4</sub></small>)(PPh<small><sub>2</sub></small>)<small><sub>2</sub></small>(μ-N)][B(C<small><sub>6</sub></small>F<small><sub>5</sub></small>)<small><sub>4</sub></small>] <strong>6′</strong> with concurrent formation of MeCl. This reactivity was extended to [(C<small><sub>2</sub></small>H<small><sub>4</sub></small>)(PPh<small><sub>2</sub></small>F)<small><sub>2</sub></small>][B(C<small><sub>6</sub></small>F<small><sub>5</sub></small>)<small><sub>4</sub></small>]<small><sub>2</sub></small><strong>7</strong> which afforded [(C<small><sub>2</sub></small>H<small><sub>4</sub></small>)(PPh<small><sub>2</sub></small>)<small><sub>2</sub></small>(μ-NR)][B(C<small><sub>6</sub></small>F<small><sub>5</sub></small>)<small><sub>4</sub></small>]<small><sub>2</sub></small> (R = Me <strong>8</strong>, CH<small><sub>2</sub></small>CHCH<small><sub>2</sub></small><strong>9</strong>, CH<small><sub>2</sub></small>Ph <strong>10</strong>) upon reaction with (Me<small><sub>3</sub></small>Si)<small><sub>2</sub></small>NR. These dications were shown to react with [nBu<small><sub>4</sub></small>N]Cl affording [(CH<small><sub>2</sub></small>PPh<small><sub>2</sub></small>)<small><sub>2</sub></small>(μ-N)][B(C<small><sub>6</sub></small>F<small><sub>5</sub></small>)<small><sub>4</sub></small>] <strong>11</strong> and the corresponding alkyl-chloride. The mechanism of these N–C bond cleavage reactions is considered.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 1","pages":" 368-375"},"PeriodicalIF":3.3000,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d4dt02990a","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Phosphazenium cations were first characterized 60 years ago and yet little is known of their reactivity. The bidentate phosphonium dicationic salts [(C6H4)(PPh2F)2][B(C6F5)4]22 and [(C6H4)(PPh2Cl)2][Cl]23 were prepared. Reaction of 2 with (Me3Si)2NMe gave the phosphazenium dication [(C6H4)(PPh2)2(μ-NMe)][B(C6F5)4]24, while reaction of 3 with two equivalents of Me2N(SiMe3) gave the related dication [(C6H4)(PPh2NMe2)2][Cl]25. Compound 3 also reacted with (Me3Si)2NH affording the monocationic salt [(C6H4)(PPh2)2(μ-N)]Cl 6, with the liberation of HCl. Interestingly 4 reacted with [nBu4N]Cl generating the related salt [(C6H4)(PPh2)2(μ-N)][B(C6F5)4] 6′ with concurrent formation of MeCl. This reactivity was extended to [(C2H4)(PPh2F)2][B(C6F5)4]27 which afforded [(C2H4)(PPh2)2(μ-NR)][B(C6F5)4]2 (R = Me 8, CH2CHCH29, CH2Ph 10) upon reaction with (Me3Si)2NR. These dications were shown to react with [nBu4N]Cl affording [(CH2PPh2)2(μ-N)][B(C6F5)4] 11 and the corresponding alkyl-chloride. The mechanism of these N–C bond cleavage reactions is considered.
期刊介绍：
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.
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