Samuel R. Lee, Brandy R. Adolph, Nattamai Bhuvanesh, Oleg V. Ozerov
{"title":"从铂(0)和金(I)的反应看一种烷/三(膦)配体的不同配位几何结构","authors":"Samuel R. Lee, Brandy R. Adolph, Nattamai Bhuvanesh, Oleg V. Ozerov","doi":"10.1016/j.poly.2024.117178","DOIUrl":null,"url":null,"abstract":"<div><p>Reactions of the tris(2-diisopropylphosphino-N-pyrrolyl)alane ligand <strong>1</strong> (AlP<sub>3</sub>) furnished an (AlP<sub>3</sub>)Pt complex <strong>2</strong>, which was determined to possess a Pt → Al interaction. Compound <strong>2</strong> reacted with CO to form the corresponding isolable adduct <strong>3</strong>. Exposure of <strong>2</strong> to H<sub>2</sub> or HD in solution resulted in the observation of equilibrium binding which favors <strong>2</strong> at room temperature, and more strongly favored the adducts <strong>2-H<sub>2</sub></strong> and <strong>2-HD</strong> at −80 °C. The presence of the Pt–H<sub>2</sub>/HD moieties is supported by low temperature NMR determination of <sup>1</sup><em>J</em><sub>PPt</sub> = 323 Hz (<strong>2-H<sub>2</sub></strong>) and <sup>1</sup><em>J</em><sub>HD</sub>=34 Hz (<strong>2-HD</strong>), ostensibly the first examples of Pt dihydrogen complexes with a trigonal bipyramidal geometry. The reaction of <strong>1</strong> with (tht)AuCl (tht = tetrahydrothiophene) generated compound <strong>4</strong> with loss of tht. An XRD study of <strong>4</strong> revealed the transfer of chloride to Al and a long separation between Al and Au coordinated by the three phosphine arms. Abstraction of chloride from <strong>4</strong> did not lead to a tripodal structure isoelectronic to <strong>2</strong>, but (according to solution NMR evidence) instead to the transfer of one of the phosphine arms to Al from Au in compound <strong>5</strong>.</p></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"262 ","pages":"Article 117178"},"PeriodicalIF":2.4000,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Varied coordination geometries of an Alane/Tris(phosphine) ligand from its Reactions with Pt(0) and Au(I)\",\"authors\":\"Samuel R. Lee, Brandy R. Adolph, Nattamai Bhuvanesh, Oleg V. Ozerov\",\"doi\":\"10.1016/j.poly.2024.117178\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Reactions of the tris(2-diisopropylphosphino-N-pyrrolyl)alane ligand <strong>1</strong> (AlP<sub>3</sub>) furnished an (AlP<sub>3</sub>)Pt complex <strong>2</strong>, which was determined to possess a Pt → Al interaction. Compound <strong>2</strong> reacted with CO to form the corresponding isolable adduct <strong>3</strong>. Exposure of <strong>2</strong> to H<sub>2</sub> or HD in solution resulted in the observation of equilibrium binding which favors <strong>2</strong> at room temperature, and more strongly favored the adducts <strong>2-H<sub>2</sub></strong> and <strong>2-HD</strong> at −80 °C. The presence of the Pt–H<sub>2</sub>/HD moieties is supported by low temperature NMR determination of <sup>1</sup><em>J</em><sub>PPt</sub> = 323 Hz (<strong>2-H<sub>2</sub></strong>) and <sup>1</sup><em>J</em><sub>HD</sub>=34 Hz (<strong>2-HD</strong>), ostensibly the first examples of Pt dihydrogen complexes with a trigonal bipyramidal geometry. The reaction of <strong>1</strong> with (tht)AuCl (tht = tetrahydrothiophene) generated compound <strong>4</strong> with loss of tht. An XRD study of <strong>4</strong> revealed the transfer of chloride to Al and a long separation between Al and Au coordinated by the three phosphine arms. Abstraction of chloride from <strong>4</strong> did not lead to a tripodal structure isoelectronic to <strong>2</strong>, but (according to solution NMR evidence) instead to the transfer of one of the phosphine arms to Al from Au in compound <strong>5</strong>.</p></div>\",\"PeriodicalId\":20278,\"journal\":{\"name\":\"Polyhedron\",\"volume\":\"262 \",\"pages\":\"Article 117178\"},\"PeriodicalIF\":2.4000,\"publicationDate\":\"2024-08-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polyhedron\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0277538724003541\",\"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":"Polyhedron","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0277538724003541","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Varied coordination geometries of an Alane/Tris(phosphine) ligand from its Reactions with Pt(0) and Au(I)
Reactions of the tris(2-diisopropylphosphino-N-pyrrolyl)alane ligand 1 (AlP3) furnished an (AlP3)Pt complex 2, which was determined to possess a Pt → Al interaction. Compound 2 reacted with CO to form the corresponding isolable adduct 3. Exposure of 2 to H2 or HD in solution resulted in the observation of equilibrium binding which favors 2 at room temperature, and more strongly favored the adducts 2-H2 and 2-HD at −80 °C. The presence of the Pt–H2/HD moieties is supported by low temperature NMR determination of 1JPPt = 323 Hz (2-H2) and 1JHD=34 Hz (2-HD), ostensibly the first examples of Pt dihydrogen complexes with a trigonal bipyramidal geometry. The reaction of 1 with (tht)AuCl (tht = tetrahydrothiophene) generated compound 4 with loss of tht. An XRD study of 4 revealed the transfer of chloride to Al and a long separation between Al and Au coordinated by the three phosphine arms. Abstraction of chloride from 4 did not lead to a tripodal structure isoelectronic to 2, but (according to solution NMR evidence) instead to the transfer of one of the phosphine arms to Al from Au in compound 5.
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Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry.
Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.
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