Jack Faller, Kevin J Chase, Jonathan Parr, Brandon Mercado
{"title":"κ2-和κ3-三吡啶胺钌配合物与吡啶基π-堆积的研究。","authors":"Jack Faller, Kevin J Chase, Jonathan Parr, Brandon Mercado","doi":"10.1107/S2053229623009415","DOIUrl":null,"url":null,"abstract":"<p><p>The reaction of tris(pyridin-2-yl)amine with [CyRuCl<sub>2</sub>]<sub>2</sub> (Cy = p-isopropyltoluene or cymene) in refluxing diglyme led to the formation of cis-[RuCl<sub>2</sub>{κ<sup>2</sup>-(2-py)<sub>3</sub>N}<sub>2</sub>]·CHCl<sub>3</sub> (1a) after recrystallization from chloroform/pentane, or cis-dichloridobis[tris(pyridin-2-yl)amine-κ<sup>2</sup>N,N']ruthenium(II) dichloromethane disolvate, [RuCl<sub>2</sub>(C<sub>15</sub>H<sub>12</sub>N<sub>4</sub>)<sub>2</sub>]·2CH<sub>2</sub>Cl<sub>2</sub> or cis-[RuCl<sub>2</sub>{κ<sup>2</sup>-(2-py)<sub>3</sub>N}<sub>2</sub>]·2CH<sub>2</sub>Cl<sub>2</sub> (1b). Treatment of 1a with one equivalent of silver(I) hexafluoridoantimonate in dichloromethane gave [RuCl{κ<sup>2</sup>-(2-py)<sub>3</sub>N}{κ<sup>3</sup>-(2-py)<sub>3</sub>N}][SbF<sub>6</sub>]·CH<sub>2</sub>Cl<sub>2</sub> (2a). Crystallization of 2a from chloroform provided chlorido[tris(pyridin-2-yl)amine-κ<sup>2</sup>N,N'][tris(pyridin-2-yl)amine-κ<sup>3</sup>N,N',N'']ruthenium(II) hexafluoridoantimonate chloroform monosolvate, [RuCl(C<sub>15</sub>H<sub>12</sub>N<sub>4</sub>)<sub>2</sub>][SbF<sub>6</sub>]·CHCl<sub>3</sub> or [RuCl{κ<sup>2</sup>-(2-py)<sub>3</sub>N}{κ<sup>3</sup>-(2-py)<sub>3</sub>N}][SbF<sub>6</sub>]·CHCl<sub>3</sub> (2b). Complex 2a reacted with a further equivalent of silver(I) hexafluoridoantimonate to give [Ru{κ<sup>3</sup>-(2-py)<sub>3</sub>N}<sub>2</sub>][SbF<sub>6</sub>]<sub>2</sub> (3). The reaction of (2-py)<sub>3</sub>N with [CyRuCl<sub>2</sub>]<sub>2</sub> in dichloromethane followed by treatment with excess sodium hexafluoridoantimonate gave the known complex [CyRuCl{κ<sup>2</sup>-(2-py)<sub>3</sub>N}][SbF<sub>6</sub>] (4). Complex 2 is a rare example of a complex containing both κ<sup>2</sup>- and κ<sup>3</sup>-(2-py)<sub>3</sub>N. Intramolecular π-stacking interactions determine the orientation of the free pyridyl in the κ<sup>2</sup> complexes. An interesting encapsulation of methylene chloride hydrogen-bonded tetramers was noted in one case.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":0.7000,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Studies of κ<sup>2</sup>- and κ<sup>3</sup>-tripyridylamine complexes of ruthenium and π-stacking by pyridyls.\",\"authors\":\"Jack Faller, Kevin J Chase, Jonathan Parr, Brandon Mercado\",\"doi\":\"10.1107/S2053229623009415\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The reaction of tris(pyridin-2-yl)amine with [CyRuCl<sub>2</sub>]<sub>2</sub> (Cy = p-isopropyltoluene or cymene) in refluxing diglyme led to the formation of cis-[RuCl<sub>2</sub>{κ<sup>2</sup>-(2-py)<sub>3</sub>N}<sub>2</sub>]·CHCl<sub>3</sub> (1a) after recrystallization from chloroform/pentane, or cis-dichloridobis[tris(pyridin-2-yl)amine-κ<sup>2</sup>N,N']ruthenium(II) dichloromethane disolvate, [RuCl<sub>2</sub>(C<sub>15</sub>H<sub>12</sub>N<sub>4</sub>)<sub>2</sub>]·2CH<sub>2</sub>Cl<sub>2</sub> or cis-[RuCl<sub>2</sub>{κ<sup>2</sup>-(2-py)<sub>3</sub>N}<sub>2</sub>]·2CH<sub>2</sub>Cl<sub>2</sub> (1b). Treatment of 1a with one equivalent of silver(I) hexafluoridoantimonate in dichloromethane gave [RuCl{κ<sup>2</sup>-(2-py)<sub>3</sub>N}{κ<sup>3</sup>-(2-py)<sub>3</sub>N}][SbF<sub>6</sub>]·CH<sub>2</sub>Cl<sub>2</sub> (2a). Crystallization of 2a from chloroform provided chlorido[tris(pyridin-2-yl)amine-κ<sup>2</sup>N,N'][tris(pyridin-2-yl)amine-κ<sup>3</sup>N,N',N'']ruthenium(II) hexafluoridoantimonate chloroform monosolvate, [RuCl(C<sub>15</sub>H<sub>12</sub>N<sub>4</sub>)<sub>2</sub>][SbF<sub>6</sub>]·CHCl<sub>3</sub> or [RuCl{κ<sup>2</sup>-(2-py)<sub>3</sub>N}{κ<sup>3</sup>-(2-py)<sub>3</sub>N}][SbF<sub>6</sub>]·CHCl<sub>3</sub> (2b). Complex 2a reacted with a further equivalent of silver(I) hexafluoridoantimonate to give [Ru{κ<sup>3</sup>-(2-py)<sub>3</sub>N}<sub>2</sub>][SbF<sub>6</sub>]<sub>2</sub> (3). The reaction of (2-py)<sub>3</sub>N with [CyRuCl<sub>2</sub>]<sub>2</sub> in dichloromethane followed by treatment with excess sodium hexafluoridoantimonate gave the known complex [CyRuCl{κ<sup>2</sup>-(2-py)<sub>3</sub>N}][SbF<sub>6</sub>] (4). Complex 2 is a rare example of a complex containing both κ<sup>2</sup>- and κ<sup>3</sup>-(2-py)<sub>3</sub>N. Intramolecular π-stacking interactions determine the orientation of the free pyridyl in the κ<sup>2</sup> complexes. An interesting encapsulation of methylene chloride hydrogen-bonded tetramers was noted in one case.</p>\",\"PeriodicalId\":7115,\"journal\":{\"name\":\"Acta Crystallographica Section C Structural Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.7000,\"publicationDate\":\"2023-12-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Acta Crystallographica Section C Structural Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1107/S2053229623009415\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2023/11/6 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Acta Crystallographica Section C Structural Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1107/S2053229623009415","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2023/11/6 0:00:00","PubModel":"Epub","JCR":"Q4","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Studies of κ2- and κ3-tripyridylamine complexes of ruthenium and π-stacking by pyridyls.
The reaction of tris(pyridin-2-yl)amine with [CyRuCl2]2 (Cy = p-isopropyltoluene or cymene) in refluxing diglyme led to the formation of cis-[RuCl2{κ2-(2-py)3N}2]·CHCl3 (1a) after recrystallization from chloroform/pentane, or cis-dichloridobis[tris(pyridin-2-yl)amine-κ2N,N']ruthenium(II) dichloromethane disolvate, [RuCl2(C15H12N4)2]·2CH2Cl2 or cis-[RuCl2{κ2-(2-py)3N}2]·2CH2Cl2 (1b). Treatment of 1a with one equivalent of silver(I) hexafluoridoantimonate in dichloromethane gave [RuCl{κ2-(2-py)3N}{κ3-(2-py)3N}][SbF6]·CH2Cl2 (2a). Crystallization of 2a from chloroform provided chlorido[tris(pyridin-2-yl)amine-κ2N,N'][tris(pyridin-2-yl)amine-κ3N,N',N'']ruthenium(II) hexafluoridoantimonate chloroform monosolvate, [RuCl(C15H12N4)2][SbF6]·CHCl3 or [RuCl{κ2-(2-py)3N}{κ3-(2-py)3N}][SbF6]·CHCl3 (2b). Complex 2a reacted with a further equivalent of silver(I) hexafluoridoantimonate to give [Ru{κ3-(2-py)3N}2][SbF6]2 (3). The reaction of (2-py)3N with [CyRuCl2]2 in dichloromethane followed by treatment with excess sodium hexafluoridoantimonate gave the known complex [CyRuCl{κ2-(2-py)3N}][SbF6] (4). Complex 2 is a rare example of a complex containing both κ2- and κ3-(2-py)3N. Intramolecular π-stacking interactions determine the orientation of the free pyridyl in the κ2 complexes. An interesting encapsulation of methylene chloride hydrogen-bonded tetramers was noted in one case.
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Acta Crystallographica Section C: Structural Chemistry is continuing its transition to a journal that publishes exciting science with structural content, in particular, important results relating to the chemical sciences. Section C is the journal of choice for the rapid publication of articles that highlight interesting research facilitated by the determination, calculation or analysis of structures of any type, other than macromolecular structures. Articles that emphasize the science and the outcomes that were enabled by the study are particularly welcomed. Authors are encouraged to include mainstream science in their papers, thereby producing manuscripts that are substantial scientific well-rounded contributions that appeal to a broad community of readers and increase the profile of the authors.
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