Ruthenium Complexes of Polyfluorocarbon Substituted Terpyridine and Mesoionic Carbene Ligands: An Interplay in CO<sub>2</sub> Reduction

Stein, Felix; Nößler, Maite; Hazari, Arijit Singha; Böser, Lisa; Walter, Robert R. M.; Liu, Huan; Klemm, Elias; Sarkar, Biprajit

doi:10.1002/chem.202300405

Chemistry A European J

2023

DOI: 10.1002/chem.202300405

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Ruthenium Complexes of Polyfluorocarbon Substituted Terpyridine and Mesoionic Carbene Ligands: An Interplay in CO₂ Reduction

Felix Stein

Maite Nößler

Arijit Singha Hazari

et al.

Abstract: In recent years terpyridines (tpy) and mesoionic carbenes (MIC) have been widely used in metal complexes. With the right combination with a metal center, both of these ligands are individually known to generate excellent catalysts for CO 2 reduction. In this study, we combine the potentials of PFC (PFC = polyfluorocarbon) substituted tpy and MIC ligands within the same platform to obtain a new class of complexes, which we investigated with respect to their structural, electrochemical and UV/Vis/NIR spectroelec… Show more

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Cited by 5 publications

References 97 publications

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Amido‐Triazole Complexes, “Normal” Triazole‐Based Imines and Metallo‐Mesoionic Imines

Rudolf,

Sarkar

2024

ChemistryEurope

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Mesoionic compounds are hugely popular in fields such as organic chemistry, organometallic chemistry and homogeneous catalysis. A new sub‐class are the mesoionic imines (MIIs). We present here 5‐amino‐4‐pyridyl‐1,2,3‐triazole as a new and versatile synthon for generating first examples of metallo‐MIIs. In this approach, we make use of metallation at the N‐pyridyl/N3‐triazole chelating pocket (instead of quarternisation of N3‐triazole) and subsequent deprotonation to generate highly versatile and tunable metallo‐MIIs. These unprecedented metallo‐MIIs contain a highly nucleophilic N‐donor site, and a tunable electrophilic metal site. Apart from displaying strong and directed H‐bonding interactions like their “classical” MII analogues, the metallo‐MIIs engage in aromatic C−F activation as well as meta−C−H activation reactions. Facile synthesis of homo and heterodincuelar complexes which contain a mixed coordinative saturation/unsaturation with these metallo‐MIIs is presented. Apart from the metallo‐MIIs we have also used 5‐amino‐4‐pyridyl‐1,2,3‐triazole as a precursor to generate the first examples of amido‐1,2,3‐triazole complexes and the first example of a “normal” (and not mesoionic) 1,2,3‐triazole based imine. Our results establish metallo‐MIIs as a versatile new class of mesoionic compounds that combine the modularity of click reactions, with the functionality of metal fragments to generate electronically ambivalent compounds with a huge potential in synthetic chemistry, catalysis and beyond.

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Amido‐Triazole Complexes, “Normal” Triazole‐Based Imines and Metallo‐Mesoionic Imines

Rudolf,

Sarkar

2024

ChemistryEurope

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Spin Crossover and Fluorine‐Specific Interactions in Metal Complexes of Terpyridines with Polyfluorocarbon Tails

Nößler

Neuman

Böser

et al. 2023

Chemistry A European J

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In coordination chemistry and materials science, terpyridine ligands are of great interest, due to their ability to form stable complexes with a broad range of transition metal ions. We report three terpyridine ligands containing different perfluorocarbon (PFC) tails on the backbone and the corresponding FeII and CoII complexes. The CoII complexes display spin crossover close to ambient temperature, and the nature of this spin transition is influenced by the length of the PFC tail on the ligand backbone. The electrochemical properties of the metal complexes were investigated with cyclic voltammetry revealing one oxidation and several reduction processes. The fluorine‐specific interactions were investigated by EPR measurements. Analysis of the EPR spectra of the complexes as microcrystalline powders and in solution reveals exchange‐narrowed spectra without resolved hyperfine splittings arising from the 59Co nucleus; this suggests complex aggregation in solution mediated by interactions of the PFC tails. Interestingly, addition of perfluoro‐octanol in different ratios to the acetonitrile solution of the sample resulted in the disruption of the F F interactions of the tails. To the best of our knowledge, this is the first investigation of fluorine‐specific interactions in metal complexes through EPR spectroscopy, as exemplified by exchange narrowing.

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Isolation, Characterization and Reactivity of Key Intermediates Relevant to Reductive (Electro)catalysis with Cp*Rh Complexes Containing Pyridyl‐MIC (MIC=Mesoionic Carbene) Ligands

Bens,

Walter,

Beerhues

et al. 2023

Chemistry A European J

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In recent years, metal complexes of pyridyl‐mesoionic carbene (MIC) ligands have been reported as excellent homogeneous and molecular electrocatalysts. In combination with group 9 metals, such ligands form highly active catalysts for hydrogenation/transfer hydrogenation/hydrosilylation catalysis and electrocatalysts for dihydrogen production. Despite such progress, very little is known about the structural/electrochemical/spectroscopic properties of crucial intermediates for such catalytic reactions with these ligands: solvato complexes, reduced complexes and hydridic species. We present here a comprehensive study involving the isolation, crystallographic characterization, electrochemical/spectroelectrochemical/theoretical investigations, and in‐situ reactivity studies of all the aforementioned crucial intermediates involving Cp*Rh and pyridyl‐MIC ligands. A detailed mechanistic study of the precatalytic activation of [RhCp*] complexes with pyridyl‐MIC ligands is presented. Intriguingly, amphiphilicity of the [RhCp*]‐hydride complexes was observed, displaying the substrate dependent transfer of H+, H∙ or H−. To the best of our knowledge, this study is the first of its kind targeting intermediates and reactive species involving metal complexes of pyridyl‐MIC ligands and investigating the interconversion amongst them.

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Ruthenium Complexes of Polyfluorocarbon Substituted Terpyridine and Mesoionic Carbene Ligands: An Interplay in CO₂ Reduction

Cited by 5 publications

References 97 publications

Amido‐Triazole Complexes, “Normal” Triazole‐Based Imines and Metallo‐Mesoionic Imines

Amido‐Triazole Complexes, “Normal” Triazole‐Based Imines and Metallo‐Mesoionic Imines

Spin Crossover and Fluorine‐Specific Interactions in Metal Complexes of Terpyridines with Polyfluorocarbon Tails

Isolation, Characterization and Reactivity of Key Intermediates Relevant to Reductive (Electro)catalysis with Cp*Rh Complexes Containing Pyridyl‐MIC (MIC=Mesoionic Carbene) Ligands

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Ruthenium Complexes of Polyfluorocarbon Substituted Terpyridine and Mesoionic Carbene Ligands: An Interplay in CO2 Reduction

Cited by 5 publications

References 97 publications

Amido‐Triazole Complexes, “Normal” Triazole‐Based Imines and Metallo‐Mesoionic Imines

Amido‐Triazole Complexes, “Normal” Triazole‐Based Imines and Metallo‐Mesoionic Imines

Spin Crossover and Fluorine‐Specific Interactions in Metal Complexes of Terpyridines with Polyfluorocarbon Tails

Isolation, Characterization and Reactivity of Key Intermediates Relevant to Reductive (Electro)catalysis with Cp*Rh Complexes Containing Pyridyl‐MIC (MIC=Mesoionic Carbene) Ligands

Contact Info

Product

Resources

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Ruthenium Complexes of Polyfluorocarbon Substituted Terpyridine and Mesoionic Carbene Ligands: An Interplay in CO₂ Reduction