{"title":"σ-胂络合物的亲电胂官能化。","authors":"Ryan M Kirk, Anthony F Hill","doi":"10.1039/d4dt01371a","DOIUrl":null,"url":null,"abstract":"<p><p>The σ-arsolido complex [Mo(AsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] is alkylated at arsenic by MeOTf to afford the pentamethylarsole complex [Mo(MeAsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)](OTf) while iodomethane affords a mixture of [Me<sub>2</sub>AsC<sub>4</sub>Me<sub>4</sub>]I, [MoMe(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)], [MoI(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] and the arsole complexes <i>cisoid</i>- and <i>transoid</i>-[MoI(MeAsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] and <i>transoid</i>-[Mo{C(O)Me}(MeAsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)], The arsole ligand in [Mo(MeAsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)](OTf) is readily liberated by NaI in acetone to afford free MeAsC<sub>4</sub>Me<sub>4</sub> and [MoI(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)]. In a similar manner, the reaction of [Mo(AsC<sub>4</sub>Ph<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] with MeI affords MeAsC<sub>4</sub>Ph<sub>4</sub> and [MoI(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)], while [Mo{AsC<sub>4</sub>(SiMe<sub>3</sub>)-2-Me<sub>2</sub>-3,4}(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] with MeOTf affords [Mo{MeAsC<sub>4</sub>(SiMe<sub>3</sub>)-2-Me<sub>2</sub>-3,4}(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)](OTf). The reaction of [Mo(AsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] with activated alkynes (RCCR: R = CF<sub>3</sub>, CO<sub>2</sub>Me) does not proceed <i>via</i> [4 + 2] <i>cyclo</i>-addition but rather electrophilic attack at arsenic followed by metallacyclisation with incorporation of a carbonyl ligand in the spirocyclic complexes [Mo{As(C<sub>4</sub>Me<sub>4</sub>)CRCRCO}(CO)<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)].</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5000,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Electrophilic As-functionalisation of σ-arsolido complexes.\",\"authors\":\"Ryan M Kirk, Anthony F Hill\",\"doi\":\"10.1039/d4dt01371a\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The σ-arsolido complex [Mo(AsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] is alkylated at arsenic by MeOTf to afford the pentamethylarsole complex [Mo(MeAsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)](OTf) while iodomethane affords a mixture of [Me<sub>2</sub>AsC<sub>4</sub>Me<sub>4</sub>]I, [MoMe(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)], [MoI(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] and the arsole complexes <i>cisoid</i>- and <i>transoid</i>-[MoI(MeAsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] and <i>transoid</i>-[Mo{C(O)Me}(MeAsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)], The arsole ligand in [Mo(MeAsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)](OTf) is readily liberated by NaI in acetone to afford free MeAsC<sub>4</sub>Me<sub>4</sub> and [MoI(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)]. In a similar manner, the reaction of [Mo(AsC<sub>4</sub>Ph<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] with MeI affords MeAsC<sub>4</sub>Ph<sub>4</sub> and [MoI(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)], while [Mo{AsC<sub>4</sub>(SiMe<sub>3</sub>)-2-Me<sub>2</sub>-3,4}(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] with MeOTf affords [Mo{MeAsC<sub>4</sub>(SiMe<sub>3</sub>)-2-Me<sub>2</sub>-3,4}(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)](OTf). The reaction of [Mo(AsC<sub>4</sub>Me<sub>4</sub>)(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] with activated alkynes (RCCR: R = CF<sub>3</sub>, CO<sub>2</sub>Me) does not proceed <i>via</i> [4 + 2] <i>cyclo</i>-addition but rather electrophilic attack at arsenic followed by metallacyclisation with incorporation of a carbonyl ligand in the spirocyclic complexes [Mo{As(C<sub>4</sub>Me<sub>4</sub>)CRCRCO}(CO)<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)].</p>\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.5000,\"publicationDate\":\"2024-07-03\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4dt01371a\",\"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://doi.org/10.1039/d4dt01371a","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
摘要
σ-胂络合物[Mo(AsC4Me4)(CO)3(η5-C5H5)]被 MeOTf 在砷处烷基化，得到五甲基胂络合物[Mo(MeAsC4Me4)(CO)3(η5-C5H5)](OTf)，而碘甲烷得到[Me2AsC4Me4]I、[MoMe(CO)3(η5-C5H5)]的混合物、[MoI(CO)3(η5-C5H5)]以及顺式和反式[MoI(MeAsC4Me4)(CO)2(η5-C5H5)]和反式[Mo{C(O)Me}(MeAsC4Me4)(CO)2(η5-C5H5)]的芳基络合物、Mo(MeAsC4Me4)(CO)3(η5-C5H5)](OTf)中的芳基配体很容易被丙酮中的 NaI 解离，从而得到游离的 MeAsC4Me4 和 [MoI(CO)3(η5-C5H5)]。类似地，[Mo(AsC4Ph4)(CO)3(η5-C5H5)] 与 MeI 反应生成 MeAsC4Ph4 和 [MoI(CO)3(η5-C5H5)]、而[Mo{AsC4(SiMe3)-2-Me2-3,4}(CO)3(η5-C5H5)]与 MeOTf 反应生成[Mo{MeAsC4(SiMe3)-2-Me2-3,4}(CO)3(η5-C5H5)](OTf)。Mo(AsC4Me4)(CO)3(η5-C5H5)]与活化炔（RCCR：R = CF3，CO2Me）的反应不是通过[4 + 2]环加成进行的，而是在砷处发生亲电攻击，然后在螺环配合物[Mo{As(C4Me4)CRCRCO}(CO)2(η5-C5H5)]中加入羰基配体进行金属化。
Electrophilic As-functionalisation of σ-arsolido complexes.
The σ-arsolido complex [Mo(AsC4Me4)(CO)3(η5-C5H5)] is alkylated at arsenic by MeOTf to afford the pentamethylarsole complex [Mo(MeAsC4Me4)(CO)3(η5-C5H5)](OTf) while iodomethane affords a mixture of [Me2AsC4Me4]I, [MoMe(CO)3(η5-C5H5)], [MoI(CO)3(η5-C5H5)] and the arsole complexes cisoid- and transoid-[MoI(MeAsC4Me4)(CO)2(η5-C5H5)] and transoid-[Mo{C(O)Me}(MeAsC4Me4)(CO)2(η5-C5H5)], The arsole ligand in [Mo(MeAsC4Me4)(CO)3(η5-C5H5)](OTf) is readily liberated by NaI in acetone to afford free MeAsC4Me4 and [MoI(CO)3(η5-C5H5)]. In a similar manner, the reaction of [Mo(AsC4Ph4)(CO)3(η5-C5H5)] with MeI affords MeAsC4Ph4 and [MoI(CO)3(η5-C5H5)], while [Mo{AsC4(SiMe3)-2-Me2-3,4}(CO)3(η5-C5H5)] with MeOTf affords [Mo{MeAsC4(SiMe3)-2-Me2-3,4}(CO)3(η5-C5H5)](OTf). The reaction of [Mo(AsC4Me4)(CO)3(η5-C5H5)] with activated alkynes (RCCR: R = CF3, CO2Me) does not proceed via [4 + 2] cyclo-addition but rather electrophilic attack at arsenic followed by metallacyclisation with incorporation of a carbonyl ligand in the spirocyclic complexes [Mo{As(C4Me4)CRCRCO}(CO)2(η5-C5H5)].
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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