Linkun Miao, Amir Yeganeh-Salman, Jason Yeung and Douglas W. Stephan
{"title":"环状磷氮阳离子的合成和 N-C 键裂解反应","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":"{\"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}","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}
Synthesis and N–C bond cleavage reactions for cyclic phosphazenium dications†
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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