Adsorption von I<sub>2</sub> durch makrocyclische Polyaza‐Dithiophenolato‐Komplexe unter Bildung von Charge‐Transfer‐Addukten

Golecki, Matthias; Beyer, Norman; Steinfeld, Gunther; Lozan, Vasile; Войтехович, Сергей В.; Sehabi, Muhamed; Möllmer, Jens; Krüger, Hans‐Jörg; Kersting, Berthold

doi:10.1002/ange.201405199

Cited by 5 publications

(2 citation statements)

References 35 publications

(18 reference statements)

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“…Kersting and coworkers showed that [Ni 2 ( L14 Me )O 2 CR] + reacted with molecular halides such as Br 2 and I 2 to form charge transfer (CT) complexes in which the dihalogen molecules were bound to one or two of the sulfur donors, depending on the nature of the carboxylate coligand ( 23 and 24 of Figure 20). [73] The CT‐compounds were relatively stable at ambient temperature with respect to the loss of gaseous I 2 and Br 2 , respectively, due to the CT interactions between the thiolate sulfur atoms and the halide. In the solid state the iodine complex exhibited secondary I⋅⋅⋅I interactions with the enclathrated iodine molecules (or the polyiodide ions).…”

Section: Compartmental Nitrogen‐based Macrocycles Incorporating Thiol...mentioning

confidence: 99%

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Fifty Years of Inorganic Biomimetic Chemistry: From the Complexation of Single Metal Cations to Polynuclear Metal Complexes by Multidentate Thiolate Ligands

2023

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This article covers 50 years of coordination chemistry of transition metal complexes and metal-sulfur aggregates involving thiolate-incorporating ligands by reviewing selected examples. The studies in the coordination chemistry of sulfur-rich ligands have been undoubtedly triggered and fed by the concomitant development of bioinorganic chemistry, particularly of iron-sulfur enzymes. The review is broken down in five sections, which examine complexes of increasing nuclearity, including binuclear complexes based on compartmental macrocyclic ligands. We show also how ligand engineering has allowed the researchers in the field to control the nuclearity of the complexes, which was a particularly difficult task for sulfurbased ligands, as thiolates show a strong tendency to coordinate to more than one metal cation at once.

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Section: Compartmental Nitrogen‐based Macrocycles Incorporating Thiol...mentioning

confidence: 99%

“… Structures of charge transfer adducts 23 and 24 formed between the thiolate complexes [Ni 2 ( L14 Me )O 2 CCH 3 ] + and [Ni 2 ( L14 Me )O 2 COCH 3 ] + with halogen molecules (X 2 =Br 2 , I 2 ). The RS→X−X linkages in 23 and 24 adopt a linear geometry [73] …”

Section: Compartmental Nitrogen‐based Macrocycles Incorporating Thiol...mentioning

confidence: 99%

Fifty Years of Inorganic Biomimetic Chemistry: From the Complexation of Single Metal Cations to Polynuclear Metal Complexes by Multidentate Thiolate Ligands

2023

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PEG‐Induced Synthesis of Coordination‐Polymer Isomers with Tunable Architectures and Iodine Capture

Zhao

Chen

Zheng

et al. 2017

Chemistry An Asian Journal

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Controllable synthesis of coordination polymer (CP) isomers and revealing their structure-property relationships remain enormous challenges. Three new supramolecular isomers have been synthesized by tuning the poly(ethylene glycol) (PEG) content in the feed. These supramolecular isomers have the same framework formula of [Cu I (tppe)] and different architectures from the classical 2D stacking framework to a 3D entangled system with the coexistence of interpenetration and polycatenation, and a 3D topological framework. Interestingly, these CPs could be utilized for capturing iodine molecules. According to multiple complementary experiments and crystallographic analyses, iodine capture is mainly based on halogen-bond interactions in the inorganic {Cu I } building blocks of the framework. The present study describes a structure-property relationship in supramolecular isomerism with distinct topological structures.

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Structure and Bonding in Nickel–Thiolate–Iodine Charge‐Transfer Complexes

Beyer

Steinfeld

Lozan

et al. 2016

Chemistry A European J

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The dinuclear nickel complexes [Ni L(μ-O CR)](ClO ) [R=Me (4), R=OMe (6)], where L is a 24-membered macrocyclic N S ligand, react readily with excess I in MeCN solution at 4 °C to form stable mono-(I ) and bis-(I ) charge-transfer (CT) adducts of the type [Ni L(μ-O CR)(I ) ] (n=1 or 2) containing linear RS-I-I linkages. Three new CT compounds, namely, [Ni L(OAc)(I )](I )(I ) (5), [Ni L(O COMe)(I )](I )⋅MeCN (7⋅MeCN), and [Ni L(O COMe)(I ) ](I )⋅MeCN (8⋅MeCN) as well as the triiodide salt [Ni L(OAc)](I ) (9) were synthesized and fully characterized. A common feature of the CT adducts is a polyiodide matrix, which surrounds the individual complex molecules, stabilized by secondary I⋅⋅⋅I interactions with the CT linkages. The scatter in both the RS-I (2.6 to 3.0 Å) and the I-I bond lengths (2.7 to 3.0 Å) is indicative of both a variable strength of the RS →I bond and a varying degree of charge transfer. An analysis of the structural parameters was undertaken accompanied by DFT calculations to quantify the donating ability of the bridging thiolate functions and to shed more light on the bonding in this rare sort of charge-transfer complexes. The stability of the CT complexes and the results of preliminary transport measurements are also reported.

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Adsorption von I₂ durch makrocyclische Polyaza‐Dithiophenolato‐Komplexe unter Bildung von Charge‐Transfer‐Addukten

Abstract: [3] Entsprechend wurde in den vergangenen Jahren eine ganze Reihe neuer CT-Komplexe vorgestellt, [4] zumeist Polyhalogenide [5] der leichteren und reaktiveren Halogene. [6,7] Nur selten finden sich darunter Addukte von Alkoholaten und Thiolaten, [8]

Cited by 5 publications

References 35 publications

Fifty Years of Inorganic Biomimetic Chemistry: From the Complexation of Single Metal Cations to Polynuclear Metal Complexes by Multidentate Thiolate Ligands

Fifty Years of Inorganic Biomimetic Chemistry: From the Complexation of Single Metal Cations to Polynuclear Metal Complexes by Multidentate Thiolate Ligands

PEG‐Induced Synthesis of Coordination‐Polymer Isomers with Tunable Architectures and Iodine Capture

Structure and Bonding in Nickel–Thiolate–Iodine Charge‐Transfer Complexes

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Adsorption von I2 durch makrocyclische Polyaza‐Dithiophenolato‐Komplexe unter Bildung von Charge‐Transfer‐Addukten

Abstract: [3] Entsprechend wurde in den vergangenen Jahren eine ganze Reihe neuer CT-Komplexe vorgestellt, [4] zumeist Polyhalogenide [5] der leichteren und reaktiveren Halogene. [6,7] Nur selten finden sich darunter Addukte von Alkoholaten und Thiolaten, [8]

Cited by 5 publications

References 35 publications

Fifty Years of Inorganic Biomimetic Chemistry: From the Complexation of Single Metal Cations to Polynuclear Metal Complexes by Multidentate Thiolate Ligands

Fifty Years of Inorganic Biomimetic Chemistry: From the Complexation of Single Metal Cations to Polynuclear Metal Complexes by Multidentate Thiolate Ligands

PEG‐Induced Synthesis of Coordination‐Polymer Isomers with Tunable Architectures and Iodine Capture

Structure and Bonding in Nickel–Thiolate–Iodine Charge‐Transfer Complexes

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Adsorption von I₂ durch makrocyclische Polyaza‐Dithiophenolato‐Komplexe unter Bildung von Charge‐Transfer‐Addukten