The First Sandwich Complex with an Octa(thioether) Coordination Sphere: Bis(maleonitrile‐tetrathia‐12‐crown‐4)silver(<scp>I</scp>)

Holdt, Hans‐Jürgen; Müller, Henrik Høeg; Pötter, M.; Kelling, Alexandra; Schilde, Uwe; Starke, Ines; Heydenreich, Matthias; Kleinpeter, Erich

doi:10.1002/ejic.200501109

Cited by 18 publications

(6 citation statements)

References 53 publications

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“…Maleonitril-tetrathia-12-krone-4 (mn12S 4 ) und Maleonitril-tetrathia-13-krone-4 (mn13S 4 ) wurden, wie von uns in [1] beschrieben, synthetisiert.…”

Section: Synthesen Ligandenunclassified

“…Im Rahmen unserer Untersuchungen mit Tetrathiakronenethern berichteten wir bereitsüber Silber(I)-Komplexe mit der Maleonitril-tetrathia-12-krone-4 (mn12S 4 ) und der Maleonitril-tetrathia-13-krone-4 (mn13S 4 [Ag 2 (mn13S 4 ) 3 ] 2+ : zwei Halbsandwicheinheiten sind uber einen dritten Liganden verbrückt, CSD-Code: DEKGEG) [1].…”

Section: Introductionunclassified

“…Die Verbindungen mn12S 4 und mn13S 4 wurden bereits früher von uns röntgenkristallographisch charakterisiert [1] (CSD-Codes: DEKFIJ, DEKFOP). Von der erstmalig synthetisierten Maleonitril-pentathia-15-krone-5 (mn15S 5 ) konnte ebenfalls eine Röntgenkri-stallstrukturanalyse angefertigt werden.…”

Section: Introductionunclassified

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Ag(I)-, Hg(II)- und Pt(II)-Komplexe von Maleonitril-thiakronenethern/ Ag(I), Hg(II) and Pt(II) Complexes with Maleonitrile-thiacrown Ethers

Müller

Kelling

Schilde

et al. 2009

Zeitschrift Für Naturforschung B

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The synthesis and single crystal X-ray structures of eight Ag I , Hg II , and Pt II complexes with the thiacrown ethers maleonitrile-tetrathia-12-crown-4 (mn12S 4 ), maleonitrile-tetrathia-13-crown-4 (mn13S 4 ), and maleonitrile-pentathia-15-crown-5 (mn15S 5 ) (1) are reported. The ligand mn15S 5 was synthesized for the first time and characterized by X-ray diffraction. With silver(I) perchlorate and silver(I) tetrafluoroborate it forms the chiral complexes [Ag(mn15S 5 )]ClO 4 ·CH 3 NO 2 (2) and [Ag(mn15S 5 )]BF 4 ·CH 3 NO 2 ·0.25H 2 O (3) with half-sandwich moieties. Ag I is located in a distorted tetrahedral coordination environment, involving three sulfur atoms of the crown cycle and a fourth one of the adjacent half-sandwich moiety, forming a helical structure. The reaction of Hg(ClO 4 ) 2 with mn13S 4 yielded the dinuclear complex [Hg 2 (mn13S 4 ) 3 ](ClO 4 ) 4 (4) containing two half-sandwich moieties with a third ligand molecule as a bridging unit. Mercury(II) chloride and mercury (II) iodide react with mn12S 4 and mn13S 4 to form complexes of the general composition [HgX 2 (L)] (X = Cl, I; L = mn12S 4 , mn13S 4 ): [HgCl 2 (mn12S 4 )] (5), [HgI 2 (mn12S 4 )] (6), [HgCl 2 (mn13S 4 )] (7) or [HgX 2 (L) 2 ] (X = I; L = mn13S 4 ): [HgI 2 (mn13S 4 ) 2 ] (8).Only one or two sulfur atoms of the ligand are involved in the complexation, and chain or ribbon structures are formed. In these compounds the HgX 2 units (X = Cl, I) are preserved, coordinated by sulfur atoms of bridging mn12S 4 or mn13S 4 ligands. In all complexes of this type, the metal atoms are not coordinated inside the cavity, but in an exocyclic mode, because the diameter of the macrocycle is too small.Additionally, the PtCl 2 complex of mn12S 4 was investigated, where Pt II is coordinated in an exocyclic mode forming the complex [PtCl 2 (mn12S 4 )] (9). Two of the four sulfur atoms of the macrocycle are bonded to the metal giving together with both chlorine atoms a square-planar coordination geometry. Together with a long-range interaction with a further sulfur atom of the macrocycle a square-pyramidal coordination environment is formed.

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“…Maleonitril-tetrathia-12-krone-4 (mn12S 4 ) und Maleonitril-tetrathia-13-krone-4 (mn13S 4 ) wurden, wie von uns in [1] beschrieben, synthetisiert.…”

Section: Synthesen Ligandenunclassified

Section: Introductionunclassified

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Ag(I)-, Hg(II)- und Pt(II)-Komplexe von Maleonitril-thiakronenethern/ Ag(I), Hg(II) and Pt(II) Complexes with Maleonitrile-thiacrown Ethers

Müller

Kelling

Schilde

et al. 2009

Zeitschrift Für Naturforschung B

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“…5. 83 The effects of pressure on the structure of the palladium(II) complex, cis-[PdCl 2 ([9]aneS 3 )] were studied, showing an intriguing switch to distorted octahedral coordination polymer with an unusual macrocycle conformation on increasing the pressure to 44 kbar. 4 Platinum(II) can be used to form molecular squares bridged by 4,4 0 -bipyridine and capped with [9]aneS 3 with triflate anions located in the square cavity.…”

Section: O P and S Macrocyclesmentioning

confidence: 99%

Macrocyclic coordination chemistry

Archibald

2007

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This chapter reviews the literature published during 2006 on macrocyclic coordination chemistry. Porphyrin ligands and supramolecular chemistry are not covered in this review as there is insufficient space and adequate coverage elsewhere, although a few examples may be included where particularly relevant. In general, the focus is on the coordination properties and reactivity of the compounds, although some applications will also be discussed, particularly in a brief section at the end of the chapter. Some representations of X-ray structures have been included to show particularly interesting coordination geometries, ion encapsulation or ligand orientation. HighlightsHighlight achievements for 2006 include characterisation of some unusual species of biological relevance that have been stabilised using the unique coordination properties of certain macrocyclic ligands, including a study of non-haem oxo-and non-oxo iron(IV) complexes and isolation of an 'end-on' nickel(II) superoxide complex. 1,2 The conversion of nitrite to nitrate is also of biological importance; a novel ruthenium(VI) oxo macrocyclic species was shown to react with nitrite to produce a coordinated nitrate anion, using the macrocycle as a stable chelator resistant to oxidative degradation. 3 Some interesting examples of solid state materials were reported involving simple macrocyclic species including a pressure sensitive compound where the coordination geometry around a palladium(II) ion was influenced by pressure due to the orientation of macrocyclic donor atoms, and a robust redox active coordination polymer built around nickel(II) cyclam units. 4,5

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“…Sandwich complexes of a crown ether with a metal cation (2:1 stoichiometry) are usually formed when the size of the crown cavity is smaller than the diameter of the metal cation. Of the different techniques used for the identification of such complexes, mass spectrometry has been widely applied . Detailed gas‐phase studies of such complexes have been reported .…”

Section: Introductionmentioning

confidence: 99%

Gas‐phase stability of sandwich complexes of crown ethers with metal cations – as studied by collision‐induced dissociation tandem mass spectrometry

Frański

2018

Rapid Comm Mass Spectrometry

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The First Sandwich Complex with an Octa(thioether) Coordination Sphere: Bis(maleonitrile‐tetrathia‐12‐crown‐4)silver(I)

Cited by 18 publications

References 53 publications

Ag(I)-, Hg(II)- und Pt(II)-Komplexe von Maleonitril-thiakronenethern/ Ag(I), Hg(II) and Pt(II) Complexes with Maleonitrile-thiacrown Ethers

Ag(I)-, Hg(II)- und Pt(II)-Komplexe von Maleonitril-thiakronenethern/ Ag(I), Hg(II) and Pt(II) Complexes with Maleonitrile-thiacrown Ethers

Macrocyclic coordination chemistry

Gas‐phase stability of sandwich complexes of crown ethers with metal cations – as studied by collision‐induced dissociation tandem mass spectrometry

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