{"title":"顺磁性过渡金属羰基配合物中Sb4四面体的稳定性。","authors":"Yu-Huei Li, Chia-Hsien Lin, Hui-Lung Chen, En-Che Yang, Minghuey Shieh","doi":"10.1021/jacs.4c13882","DOIUrl":null,"url":null,"abstract":"<p><p>We present a straightforward synthetic route to the novel chromium carbonyl-stabilized paramagnetic Sb<sub>4</sub>-based cluster [Et<sub>4</sub>N]<sub>4</sub>[Sb<sub>4</sub>Cr<sub>6</sub>(CO)<sub>28</sub>] ([Et<sub>4</sub>N]<sub>4</sub>[<b>1</b>]), which represented a rare example of the intact Sb<sub>4</sub> tetrahedron structurally characterized in the solid state. Complex <b>1</b> exhibited versatile reactivities toward groups 7-9 metal carbonyls, dioxygen, or [Cu(MeCN)<sub>4</sub>][BF<sub>4</sub>] to form selective orbital-controlled Sb<sub>4</sub>-based products, including transmetalated paramagnetic complexes [Et<sub>4</sub>N]<sub>4</sub>[Sb<sub>4</sub>Cr<sub>5</sub>Mn(CO)<sub>28</sub>]Br ([Et<sub>4</sub>N]<sub>4</sub>[<b>1-Mn</b>]Br), [Et<sub>4</sub>N]<sub>4</sub>[Sb<sub>4</sub>Cr<sub>2</sub>Fe<sub>6</sub>(CO)<sub>30</sub>] ([Et<sub>4</sub>N]<sub>4</sub>[<b>1-Fe</b>]), and [Et<sub>4</sub>N]<sub>2</sub>[Sb<sub>4</sub>Cr<sub>4</sub>Co<sub>4</sub>(CO)<sub>31</sub>] ([Et<sub>4</sub>N]<sub>2</sub>[<b>1-Co</b>]), the dioxygen-activated paramagnetic cluster [Et<sub>4</sub>N]<sub>4</sub>[O<sub>2</sub>Sb<sub>4</sub>Cr<sub>6</sub>(CO)<sub>28</sub>] ([Et<sub>4</sub>N]<sub>4</sub>[<b>1-O</b><sub><b>2</b></sub>]), or the spin-quenched complex [Et<sub>4</sub>N]<sub>2</sub>[Sb<sub>4</sub>Cr<sub>6</sub>(CO)<sub>28</sub>] ([Et<sub>4</sub>N]<sub>2</sub>[<b>2</b>]), respectively. The structural nature, bonding properties, paramagnetism, and semiconductivity of these unprecedented transition metal carbonyl-protected Sb<sub>4</sub>-based clusters were further realized with DFT calculations.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"9043-9048"},"PeriodicalIF":15.6000,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Stabilization of Sb<sub>4</sub> Tetrahedra in Paramagnetic Transition Metal Carbonyl Complexes.\",\"authors\":\"Yu-Huei Li, Chia-Hsien Lin, Hui-Lung Chen, En-Che Yang, Minghuey Shieh\",\"doi\":\"10.1021/jacs.4c13882\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>We present a straightforward synthetic route to the novel chromium carbonyl-stabilized paramagnetic Sb<sub>4</sub>-based cluster [Et<sub>4</sub>N]<sub>4</sub>[Sb<sub>4</sub>Cr<sub>6</sub>(CO)<sub>28</sub>] ([Et<sub>4</sub>N]<sub>4</sub>[<b>1</b>]), which represented a rare example of the intact Sb<sub>4</sub> tetrahedron structurally characterized in the solid state. Complex <b>1</b> exhibited versatile reactivities toward groups 7-9 metal carbonyls, dioxygen, or [Cu(MeCN)<sub>4</sub>][BF<sub>4</sub>] to form selective orbital-controlled Sb<sub>4</sub>-based products, including transmetalated paramagnetic complexes [Et<sub>4</sub>N]<sub>4</sub>[Sb<sub>4</sub>Cr<sub>5</sub>Mn(CO)<sub>28</sub>]Br ([Et<sub>4</sub>N]<sub>4</sub>[<b>1-Mn</b>]Br), [Et<sub>4</sub>N]<sub>4</sub>[Sb<sub>4</sub>Cr<sub>2</sub>Fe<sub>6</sub>(CO)<sub>30</sub>] ([Et<sub>4</sub>N]<sub>4</sub>[<b>1-Fe</b>]), and [Et<sub>4</sub>N]<sub>2</sub>[Sb<sub>4</sub>Cr<sub>4</sub>Co<sub>4</sub>(CO)<sub>31</sub>] ([Et<sub>4</sub>N]<sub>2</sub>[<b>1-Co</b>]), the dioxygen-activated paramagnetic cluster [Et<sub>4</sub>N]<sub>4</sub>[O<sub>2</sub>Sb<sub>4</sub>Cr<sub>6</sub>(CO)<sub>28</sub>] ([Et<sub>4</sub>N]<sub>4</sub>[<b>1-O</b><sub><b>2</b></sub>]), or the spin-quenched complex [Et<sub>4</sub>N]<sub>2</sub>[Sb<sub>4</sub>Cr<sub>6</sub>(CO)<sub>28</sub>] ([Et<sub>4</sub>N]<sub>2</sub>[<b>2</b>]), respectively. The structural nature, bonding properties, paramagnetism, and semiconductivity of these unprecedented transition metal carbonyl-protected Sb<sub>4</sub>-based clusters were further realized with DFT calculations.</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":\" \",\"pages\":\"9043-9048\"},\"PeriodicalIF\":15.6000,\"publicationDate\":\"2025-03-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/jacs.4c13882\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2025/3/11 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.4c13882","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/3/11 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Stabilization of Sb4 Tetrahedra in Paramagnetic Transition Metal Carbonyl Complexes.
We present a straightforward synthetic route to the novel chromium carbonyl-stabilized paramagnetic Sb4-based cluster [Et4N]4[Sb4Cr6(CO)28] ([Et4N]4[1]), which represented a rare example of the intact Sb4 tetrahedron structurally characterized in the solid state. Complex 1 exhibited versatile reactivities toward groups 7-9 metal carbonyls, dioxygen, or [Cu(MeCN)4][BF4] to form selective orbital-controlled Sb4-based products, including transmetalated paramagnetic complexes [Et4N]4[Sb4Cr5Mn(CO)28]Br ([Et4N]4[1-Mn]Br), [Et4N]4[Sb4Cr2Fe6(CO)30] ([Et4N]4[1-Fe]), and [Et4N]2[Sb4Cr4Co4(CO)31] ([Et4N]2[1-Co]), the dioxygen-activated paramagnetic cluster [Et4N]4[O2Sb4Cr6(CO)28] ([Et4N]4[1-O2]), or the spin-quenched complex [Et4N]2[Sb4Cr6(CO)28] ([Et4N]2[2]), respectively. The structural nature, bonding properties, paramagnetism, and semiconductivity of these unprecedented transition metal carbonyl-protected Sb4-based clusters were further realized with DFT calculations.
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