Chalcogen Bonding Induced Tetraselenides from Twisted Diselenides

Vaddamanu, Moulali; Prabusankar, Ganesan

doi:10.1002/ejic.202000275

Cited by 15 publications

(5 citation statements)

References 45 publications

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“…Most likely, dimerization of the selenium adducts occurs (Scheme 1), which has been proposed [8] and observed before for NHC sulfur adducts, [9] and during electrochemical synthesis of disulfides [10] . Recently, 1,2,3‐triazolin di‐ and tetraselinides have been isolated after chemical oxidation [11] …”

Section: Resultsmentioning

confidence: 64%

Directed Design of a Au^I Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Beerhues

Neubrand

Sobottka

et al. 2021

Chemistry A European J

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Carbene‐based radicals are important for both fundamental and applied chemical research. Herein, extensive electrochemical investigations of nine different 1,2,3‐triazolylidene selenium adducts are reported. It is found that the half‐wave potentials of the first reduction of the selones correlate with their calculated LUMO levels and the LUMO levels of the corresponding triazolylidene‐based mesoionic carbenes (MICs). Furthermore, unexpected quasi‐reversibility of the reduction of two triazoline selones, exhibiting comparable reduction potentials, was discovered. Through UV/Vis/NIR and EPR spectroelectrochemical investigations supported by DFT calculations, the radical anion was unambiguously assigned to be triazoline centered. This electrochemical behavior was transferred to a triazolylidene‐type MIC‐gold phenyl complex resulting in a MIC‐radical coordinated AuI species. Apart from UV‐Vis‐NIR and EPR spectroelectrochemical investigations of the reduction, the reduced gold‐coordinated MIC radical complex was also formed in situ in the bulk through chemical reduction. This is the first report of a monodentate triazolylidene‐based MIC ligand that can be reduced to its anion radical in a metal complex. The results presented here provide design principles for stabilizing radicals based on MICs.

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Section: Resultsmentioning

confidence: 64%

Directed Design of a Au^I Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Beerhues

Neubrand

Sobottka

et al. 2021

Chemistry A European J

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“…The sterically controlled oxidation of the triazoline selones 183 in the presence of a copper(II) salt yielded MIC-stabilized di- and tetraselenides (Scheme ). The reaction product is probably dependent on the steric bulk of the MIC substituents. The MIC selenium adducts were also investigated via 77 Se NMR spectroscopy to gauge the π-acceptor properties of the corresponding triazolylidenes (see section on donor/acceptor properties above). , Furthermore, the electrochemical properties of the MIC selenium adducts were investigated, and it was shown that, with appropriate substituents, reduction of these adducts, which are triazolylidene-based, is reversible.…”

Section: Main Group Educts Of Micsmentioning

confidence: 89%

“…The sterically controlled oxidation of the triazoline selones 183 in the presence of a copper(II) salt yielded MIC-stabilized di-and tetraselenides (Scheme 38). 146 The reaction product is probably dependent on the steric bulk of the MIC substituents. The MIC selenium adducts were also investigated via 77 Se NMR spectroscopy to gauge the π-acceptor properties of the corresponding triazolylidenes (see section on donor/acceptor properties above).…”

Section: Group 16mentioning

confidence: 99%

Chemistry of Compounds Based on 1,2,3-Triazolylidene-Type Mesoionic Carbenes

Maity

Sarkar

2021

JACS Au

106

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Mesoionic carbenes (MICs) of the 1,2,3-triazolylidene type have established themselves as a popular class of compounds over the past decade. Primary reasons for this popularity are their modular synthesis and their strong donor properties. While such MICs have mostly been used in combination with transition metals, the past few years have also seen their utility together with main group elements. In this paper, we present an overview of the recent developments on this class of compounds that include, among others, (i) cationic and anionic MIC ligands, (ii) the donor/acceptor properties of these ligands with a focus on the several methods that are known for estimating such donor/acceptor properties, (iii) a detailed overview of 3d metal complexes and main group compounds with these MIC ligands, (iv) results on the redox and photophysical properties of compounds based on MIC ligands, and (v) an overview on electrocatalysis, redox-switchable catalysis, and small-molecule activation to highlight the applications of compounds based on MIC ligands in contemporary chemistry. By discussing several aspects from the synthetic, spectroscopic, and application point of view of these classes of compounds, we highlight the state of the art of compounds containing MICs and present a perspective for future research in this field.

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“…One might expect either aurophilic [11] Au … Au or chalcogenophilic [12] Se … Se intermolecular bonding for these di/mono‐cationic Se/Au species 2 b , 3 and 4 , however, no such intermolecular secondary bonds were observed (compare Supporting Information), most likely due to the position of the tetraphenylborate or hexafluoridophosphate counterions in the crystal lattice. In comparison, NHC−Se gold(I) complexes containing bulky wingtip substituents display dimeric solid state structures with weak Se … Se interactions [10a] …”

Section: Methodsmentioning

confidence: 99%

“…In comparison, NHC−Se gold(I) complexes containing bulky wingtip substituents display dimeric solid state structures with weak Se … Se interactions. [10a] …”

mentioning

confidence: 99%

Cobaltoceniumselenolate Gold(I) Complexes: Synthesis, Spectroscopic, Structural and Anticancer Properties

et al. 2021

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Cobaltoceniumselenolate is an unusual, highly air‐sensitive, mesoionic compound containing a very soft anionic selenium donor atom. Here we explore its coordination chemistry with Au(I) metal centers and show that its hetero‐ and homoleptic gold complexes are highly colored, air‐stable compounds, which were characterized by 1 H/ 13 C/ 31 P/ 77 Se NMR, IR, UV‐Vis, HR‐MS and single crystal XRD. Cytotoxicity of these polar, water‐soluble complexes was studied against various standard cancer cell lines (A549MDA‐MB‐231, HT‐29) revealing good anticancer activity of all three complexes.

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Chalcogen Bonding Induced Tetraselenides from Twisted Diselenides

Cited by 15 publications

References 45 publications

Directed Design of a Au^I Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Directed Design of a Au^I Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Chemistry of Compounds Based on 1,2,3-Triazolylidene-Type Mesoionic Carbenes

Cobaltoceniumselenolate Gold(I) Complexes: Synthesis, Spectroscopic, Structural and Anticancer Properties

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Chalcogen Bonding Induced Tetraselenides from Twisted Diselenides

Cited by 15 publications

References 45 publications

Directed Design of a AuI Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Directed Design of a AuI Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Chemistry of Compounds Based on 1,2,3-Triazolylidene-Type Mesoionic Carbenes

Cobaltoceniumselenolate Gold(I) Complexes: Synthesis, Spectroscopic, Structural and Anticancer Properties

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Directed Design of a Au^I Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Directed Design of a Au^I Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations