{"title":"在[Re2(CO)8(THF)2]络合物的钌位点轻松激活 CH 芳基键和 OH 键","authors":"","doi":"10.1016/j.ica.2024.122384","DOIUrl":null,"url":null,"abstract":"<div><div>The activation of small molecules is a topic of great interest and previously we reported on the easy activation of different types of E<img>H bonds at the dinuclear complex [Re<sub>2</sub>(CO)<sub>8</sub>(THF)<sub>2</sub>] (<strong>1</strong>) where labile THF molecules coordinate to adjacent rhenium(0) atoms. Here we extend the reactivity of <strong>1</strong> reporting on the oxidative addition of benzene and toluene at room temperature to give [Re<sub>2</sub>(μ-H)(μ-κ<em>C</em>-Ar)(CO)<sub>8</sub>], Ar = −C<sub>6</sub>H<sub>5</sub> (<strong>2</strong>) and −C<sub>6</sub>H<sub>4</sub>Me (<strong>3</strong>). Compound <strong>3</strong> is a new example of μ-κ<em>C</em>-Ar dinuclear rhenium complex and has been obtained as <em>para</em> and <em>meta</em> isomers (<strong>3a</strong>,<strong>b</strong>). It is known from the literature that <strong>2</strong> can activate arenes and heteroarenes via reductive elimination of benzene and oxidative addition of C<img>H bonds to the dinuclear fragment. Here we have studied the reaction of <strong>2</strong> with C<sub>6</sub>D<sub>6</sub> and H<sub>2</sub>C<img>C(H)Ph and determined the kinetic constants by <sup>1</sup>H NMR (1.4 × 10<sup>−5</sup> s<sup>−1</sup> at 308 K and 1.1 × 10<sup>−5</sup> s<sup>−1</sup> at 298 K, respectively). The results indicate that the rate-determining step of the reaction is the reductive elimination of benzene, while the oxidative addition is fast. Water and methanol react with <strong>1</strong> in toluene at room temperature to give the hydroxo and methoxo hydrido complexes [Re<sub>2</sub>(μ-H)(μ-OR)(CO)<sub>8</sub>], R<img>H (<strong>5</strong>) and CH<sub>3</sub> (<strong>6</strong>). On reacting <strong>1</strong> with water in deuterated toluene, and monitoring by <sup>1</sup>H/<sup>2</sup>H NMR, a preferential deuteration of the hydride site to give [Re<sub>2</sub>(μ-D)(μ-OH)(CO)<sub>8</sub>] is evidenced. This finding excludes the oxidative addition of water on the dinuclear “Re<sub>2</sub>(CO)<sub>8</sub>” fragment while supporting a heterolytic addition of water via protonation at the µ-κ<em>C</em>-tolyl group, elimination of toluene and addition of OH<sup>−</sup>. Single crystal X-ray diffraction analyses have been performed for complexes <strong>3a</strong>, <strong>5</strong> and <strong>6</strong> and their solid state structures have been determined. In particular, the crystal structure of <strong>5</strong> results in a new polymorphic form (<strong>5b</strong>) and it is discussed in comparison with the already known one (<strong>5a</strong>).</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Facile CH aryl and OH bonds activation at dirhenium site of [Re2(CO)8(THF)2] complex\",\"authors\":\"\",\"doi\":\"10.1016/j.ica.2024.122384\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The activation of small molecules is a topic of great interest and previously we reported on the easy activation of different types of E<img>H bonds at the dinuclear complex [Re<sub>2</sub>(CO)<sub>8</sub>(THF)<sub>2</sub>] (<strong>1</strong>) where labile THF molecules coordinate to adjacent rhenium(0) atoms. Here we extend the reactivity of <strong>1</strong> reporting on the oxidative addition of benzene and toluene at room temperature to give [Re<sub>2</sub>(μ-H)(μ-κ<em>C</em>-Ar)(CO)<sub>8</sub>], Ar = −C<sub>6</sub>H<sub>5</sub> (<strong>2</strong>) and −C<sub>6</sub>H<sub>4</sub>Me (<strong>3</strong>). Compound <strong>3</strong> is a new example of μ-κ<em>C</em>-Ar dinuclear rhenium complex and has been obtained as <em>para</em> and <em>meta</em> isomers (<strong>3a</strong>,<strong>b</strong>). It is known from the literature that <strong>2</strong> can activate arenes and heteroarenes via reductive elimination of benzene and oxidative addition of C<img>H bonds to the dinuclear fragment. Here we have studied the reaction of <strong>2</strong> with C<sub>6</sub>D<sub>6</sub> and H<sub>2</sub>C<img>C(H)Ph and determined the kinetic constants by <sup>1</sup>H NMR (1.4 × 10<sup>−5</sup> s<sup>−1</sup> at 308 K and 1.1 × 10<sup>−5</sup> s<sup>−1</sup> at 298 K, respectively). The results indicate that the rate-determining step of the reaction is the reductive elimination of benzene, while the oxidative addition is fast. Water and methanol react with <strong>1</strong> in toluene at room temperature to give the hydroxo and methoxo hydrido complexes [Re<sub>2</sub>(μ-H)(μ-OR)(CO)<sub>8</sub>], R<img>H (<strong>5</strong>) and CH<sub>3</sub> (<strong>6</strong>). On reacting <strong>1</strong> with water in deuterated toluene, and monitoring by <sup>1</sup>H/<sup>2</sup>H NMR, a preferential deuteration of the hydride site to give [Re<sub>2</sub>(μ-D)(μ-OH)(CO)<sub>8</sub>] is evidenced. This finding excludes the oxidative addition of water on the dinuclear “Re<sub>2</sub>(CO)<sub>8</sub>” fragment while supporting a heterolytic addition of water via protonation at the µ-κ<em>C</em>-tolyl group, elimination of toluene and addition of OH<sup>−</sup>. Single crystal X-ray diffraction analyses have been performed for complexes <strong>3a</strong>, <strong>5</strong> and <strong>6</strong> and their solid state structures have been determined. In particular, the crystal structure of <strong>5</strong> results in a new polymorphic form (<strong>5b</strong>) and it is discussed in comparison with the already known one (<strong>5a</strong>).</div></div>\",\"PeriodicalId\":13599,\"journal\":{\"name\":\"Inorganica Chimica Acta\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-09-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganica Chimica Acta\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0020169324004754\",\"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":"Inorganica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0020169324004754","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Facile CH aryl and OH bonds activation at dirhenium site of [Re2(CO)8(THF)2] complex
The activation of small molecules is a topic of great interest and previously we reported on the easy activation of different types of EH bonds at the dinuclear complex [Re2(CO)8(THF)2] (1) where labile THF molecules coordinate to adjacent rhenium(0) atoms. Here we extend the reactivity of 1 reporting on the oxidative addition of benzene and toluene at room temperature to give [Re2(μ-H)(μ-κC-Ar)(CO)8], Ar = −C6H5 (2) and −C6H4Me (3). Compound 3 is a new example of μ-κC-Ar dinuclear rhenium complex and has been obtained as para and meta isomers (3a,b). It is known from the literature that 2 can activate arenes and heteroarenes via reductive elimination of benzene and oxidative addition of CH bonds to the dinuclear fragment. Here we have studied the reaction of 2 with C6D6 and H2CC(H)Ph and determined the kinetic constants by 1H NMR (1.4 × 10−5 s−1 at 308 K and 1.1 × 10−5 s−1 at 298 K, respectively). The results indicate that the rate-determining step of the reaction is the reductive elimination of benzene, while the oxidative addition is fast. Water and methanol react with 1 in toluene at room temperature to give the hydroxo and methoxo hydrido complexes [Re2(μ-H)(μ-OR)(CO)8], RH (5) and CH3 (6). On reacting 1 with water in deuterated toluene, and monitoring by 1H/2H NMR, a preferential deuteration of the hydride site to give [Re2(μ-D)(μ-OH)(CO)8] is evidenced. This finding excludes the oxidative addition of water on the dinuclear “Re2(CO)8” fragment while supporting a heterolytic addition of water via protonation at the µ-κC-tolyl group, elimination of toluene and addition of OH−. Single crystal X-ray diffraction analyses have been performed for complexes 3a, 5 and 6 and their solid state structures have been determined. In particular, the crystal structure of 5 results in a new polymorphic form (5b) and it is discussed in comparison with the already known one (5a).
期刊介绍:
Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews.
Topics covered include:
• chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies;
• synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs);
• reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models;
• applications of inorganic compounds, metallodrugs and molecule-based materials.
Papers composed primarily of structural reports will typically not be considered for publication.