{"title":"[Fe2[(μ-SeCH2)2NH](CN)2(CO)4]2-及其相关硒酸铁的合成","authors":"Xin Yu, Toby J Woods, Thomas B Rauchfuss","doi":"10.1021/acs.organomet.4c00457","DOIUrl":null,"url":null,"abstract":"<p><p>The dianion [Fe<sub>2</sub>[(μ-SeCH<sub>2</sub>)<sub>2</sub>NH](CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>2-</sup> ([<b>2</b>]<sup>2-</sup>) is of interest for the preparation of the selenide analog of the active site of the [FeFe]-hydrogenases. The obvious route for its synthesis by cyanation of Fe<sub>2</sub>[(μ-SeCH<sub>2</sub>)<sub>2</sub>NH](CO)<sub>6</sub> (<b>3</b>) fails for reasons that this paper explains and resolves. We show that CN<sup>-</sup> cleaves Se-C bonds in <b>3</b>. For example, treatment of Fe<sub>2</sub>[(μ-SeCH<sub>2</sub>)<sub>2</sub>NH](CO)<sub>6</sub> with NEt<sub>4</sub>CN followed by CH<sub>3</sub>I gives substantial amounts of Fe<sub>2</sub>(μ-SeCH<sub>3</sub>)<sub>2</sub>(CO)<sub>6</sub>. Authentic [<b>2</b>]<sup>2-</sup> can be obtained by cyanation of Fe<sub>2</sub>[(μ-SeCH<sub>2</sub>)<sub>2</sub>NH](CO)<sub>5</sub>(pyridine). The <sup>77</sup>Se NMR data for [<b>2</b>]<sup>2-</sup> and <b>3</b> are reevaluated and explained. Attempts to prepare Fe<sub>2</sub>[(μ-SeCH<sub>2</sub>)<sub>2</sub>NH](PPh<sub>3</sub>)<sub>2</sub>(CO)<sub>4</sub> (<b>9</b>) by Me<sub>3</sub>NO-induced decarbonylation of <b>3</b> also suffers from degradation of the organoselenium ligand. Complex <b>9</b> was prepared instead by photosubstitution. The protonation of [<b>2</b>]<sup>2-</sup> and [Fe<sub>2</sub>[(μ-SCH<sub>2</sub>)<sub>2</sub>NH](CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>2-</sup> are compared: the selenium compounds are more basic. The structure of [HFe<sub>2</sub>[(μ-SCH<sub>2</sub>)<sub>2</sub>NH](CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>-</sup> was determined crystallographically.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"307-314"},"PeriodicalIF":2.5000,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11734109/pdf/","citationCount":"0","resultStr":"{\"title\":\"Synthesis of [Fe<sub>2</sub>[(μ-SeCH<sub>2</sub>)<sub>2</sub>NH](CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>2-</sup> and Related Iron Selenoates.\",\"authors\":\"Xin Yu, Toby J Woods, Thomas B Rauchfuss\",\"doi\":\"10.1021/acs.organomet.4c00457\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The dianion [Fe<sub>2</sub>[(μ-SeCH<sub>2</sub>)<sub>2</sub>NH](CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>2-</sup> ([<b>2</b>]<sup>2-</sup>) is of interest for the preparation of the selenide analog of the active site of the [FeFe]-hydrogenases. The obvious route for its synthesis by cyanation of Fe<sub>2</sub>[(μ-SeCH<sub>2</sub>)<sub>2</sub>NH](CO)<sub>6</sub> (<b>3</b>) fails for reasons that this paper explains and resolves. We show that CN<sup>-</sup> cleaves Se-C bonds in <b>3</b>. For example, treatment of Fe<sub>2</sub>[(μ-SeCH<sub>2</sub>)<sub>2</sub>NH](CO)<sub>6</sub> with NEt<sub>4</sub>CN followed by CH<sub>3</sub>I gives substantial amounts of Fe<sub>2</sub>(μ-SeCH<sub>3</sub>)<sub>2</sub>(CO)<sub>6</sub>. Authentic [<b>2</b>]<sup>2-</sup> can be obtained by cyanation of Fe<sub>2</sub>[(μ-SeCH<sub>2</sub>)<sub>2</sub>NH](CO)<sub>5</sub>(pyridine). The <sup>77</sup>Se NMR data for [<b>2</b>]<sup>2-</sup> and <b>3</b> are reevaluated and explained. Attempts to prepare Fe<sub>2</sub>[(μ-SeCH<sub>2</sub>)<sub>2</sub>NH](PPh<sub>3</sub>)<sub>2</sub>(CO)<sub>4</sub> (<b>9</b>) by Me<sub>3</sub>NO-induced decarbonylation of <b>3</b> also suffers from degradation of the organoselenium ligand. Complex <b>9</b> was prepared instead by photosubstitution. The protonation of [<b>2</b>]<sup>2-</sup> and [Fe<sub>2</sub>[(μ-SCH<sub>2</sub>)<sub>2</sub>NH](CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>2-</sup> are compared: the selenium compounds are more basic. The structure of [HFe<sub>2</sub>[(μ-SCH<sub>2</sub>)<sub>2</sub>NH](CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>-</sup> was determined crystallographically.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":\"44 1\",\"pages\":\"307-314\"},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-12-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11734109/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.organomet.4c00457\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2025/1/13 0:00:00\",\"PubModel\":\"eCollection\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.organomet.4c00457","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/1/13 0:00:00","PubModel":"eCollection","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Synthesis of [Fe2[(μ-SeCH2)2NH](CN)2(CO)4]2- and Related Iron Selenoates.
The dianion [Fe2[(μ-SeCH2)2NH](CN)2(CO)4]2- ([2]2-) is of interest for the preparation of the selenide analog of the active site of the [FeFe]-hydrogenases. The obvious route for its synthesis by cyanation of Fe2[(μ-SeCH2)2NH](CO)6 (3) fails for reasons that this paper explains and resolves. We show that CN- cleaves Se-C bonds in 3. For example, treatment of Fe2[(μ-SeCH2)2NH](CO)6 with NEt4CN followed by CH3I gives substantial amounts of Fe2(μ-SeCH3)2(CO)6. Authentic [2]2- can be obtained by cyanation of Fe2[(μ-SeCH2)2NH](CO)5(pyridine). The 77Se NMR data for [2]2- and 3 are reevaluated and explained. Attempts to prepare Fe2[(μ-SeCH2)2NH](PPh3)2(CO)4 (9) by Me3NO-induced decarbonylation of 3 also suffers from degradation of the organoselenium ligand. Complex 9 was prepared instead by photosubstitution. The protonation of [2]2- and [Fe2[(μ-SCH2)2NH](CN)2(CO)4]2- are compared: the selenium compounds are more basic. The structure of [HFe2[(μ-SCH2)2NH](CN)2(CO)4]- was determined crystallographically.
期刊介绍：
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.
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