Studies of κ²- and κ³-tripyridylamine complexes of ruthenium and π-stacking by pyridyls.

IF 0.7 4区化学 Q4 CHEMISTRY, MULTIDISCIPLINARY Acta Crystallographica Section C Structural Chemistry Pub Date : 2023-12-01 Epub Date: 2023-11-06 DOI:10.1107/S2053229623009415

Jack Faller, Kevin J Chase, Jonathan Parr, Brandon Mercado

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Abstract

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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κ2-和κ3-三吡啶胺钌配合物与吡啶基π-堆积的研究。

三（吡啶-2-基）胺与[CyRuCl2]2（Cy=对异丙基甲苯或cymene）在回流二甘醇中的反应导致从氯仿/戊烷重结晶后形成顺式-[RuCl2{κ2-（2-py）3N}2]·CHCl3（1a），或顺式二氯双[三（吡啶2-基）胺-κ2N，N']二氯甲烷二溶剂钌（II）、[RuCl2（C15H12N4）2]·2CH2Cl2或顺式-[LuCl2[κ2-（2-py）3N}2]·2CH2Cl2（1b）。用一当量的六氟锑酸银（I）在二氯甲烷中处理1a，得到[RuCl{κ2-（2-py）3N}{κ3-（2-py3N}][SbF6]·CH2Cl2（2a）。2a从氯仿中结晶提供了氯[三（吡啶-2-基）胺-κ2N，N'][三（吡啶2-基）胺–κ3N，N'，N']六氟锑酸钌（II）氯仿单溶剂，[RuCl（C15H12N4）2][SbF6]·CHCl3或[RuCl｛κ2-（2-py）3N}｛κ3-（2-py。配合物2a与另一当量的六氟锑酸银（I）反应，得到[Ru｛κ3-（2-py）3N｝2][SbF6]2（3）。（2-py）3N与[CyRuCl2]2在二氯甲烷中反应，然后用过量的六氟锑酸钠处理，得到已知的络合物[CyRuCl｛κ。复合物2是同时含有κ2-和κ3-（2-py）3N的复合物的罕见例子。分子内π-堆积相互作用决定了κ2复合物中游离吡啶基的取向。在一个案例中注意到二氯甲烷氢键四聚体的有趣封装。

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来源期刊

Acta Crystallographica Section C Structural Chemistry CHEMISTRY, MULTIDISCIPLINARYCRYSTALLOGRAPH-CRYSTALLOGRAPHY

CiteScore

1.60

自引率

12.50%

发文量

148

期刊介绍： 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.