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

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

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

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 Au-I 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

Impact of Bidentate Pyridyl-Mesoionic Carbene Ligands: Structural, (Spectro)Electrochemical, Photophysical, and Theoretical Investigations on Ruthenium(II) Complexes

We present here new synthetic strategies for the isolation of a series of Ru(II) complexes with pyridyl-mesoionic carbene ligands (MIC) of the 1,2,3-triazole-5-ylidene type, in which the bpy ligands (bpy = 2,2′-bipyridine) of the archetypical [Ru(bpy)3]2+ have been successively replaced by one, two, or three pyridyl-MIC ligands. Three new complexes have been isolated and investigated via NMR spectroscopy and single-crystal X-ray diffraction analysis. The incorporation of one MIC unit shifts the potential of the metal-centered oxidation about 160 mV to more cathodic potential in cyclic voltammetry, demonstrating the extraordinary σ-donor ability of the pyridyl-MIC ligand, while the π-acceptor capacities are dominated by the bpy ligand, as indicated by electron paramagnetic resonance spectroelectrochemistry (EPR-SEC). The replacement of all bpy ligands by the pyridyl-MIC ligand results in an anoidic shift of the ligand-centered reduction by 390 mV compared to the well-established [Ru(bpy)3]2+ complex. In addition, UV/vis/NIR-SEC in combination with theoretical calculations provided detailed insights into the electronic structures of the respective redox states, taking into account the total number of pyridyl-MIC ligands incorporated in the Ru(II) complexes. The luminescence quantum yield and lifetimes were determined by time-resolved absorption and emission spectroscopy. An estimation of the excited state redox potentials conclusively showed that the pyridyl-MIC ligand can tune the photoredox activity of the isolated complexes to stronger photoreductants. These observations can provide new strategies for the design of photocatalysts and photosensitizers based on MICs

Chromium(0) and Molydenum(0) Complexes with a Pyridyl-Mesoionic Carbene Ligand: Structural, (Spectro)electrochemical, Photochemical, and Theoretical Investigations

This work reports on the synthesis and in-depth electrochemical and photochemical characterization of two chromium(0) and molydenum(0) metal complexes with bidentate pyridyl-mesoionic carbene (MIC) ligands of the 1,2,3-triazol-5-ylidene type and carbonyl coligands. Metal complexes with MIC ligands have turned out to have very promising electrocatalytic and photochemical properties, but examples of MIC-containing complexes with early-transition-metal centers remain extremely rare. The electrochemistry of these new MIC complexes was studied by cyclic voltammetry and especially spectroelectrochemistry in the IR region consistent with a mainly metal-centered oxidation, which is fully reversible in the case of the chromium(0) complex. At the same time, the two reduction steps are predominantly ligand-centered according to the observed near-IR absorbance, with the first reduction step being reversible for both systems. The results of the electron paramagnetic resonance studies on the oxidized and reduced species confirm the IR spectroelectrochemistry experiments. The photochemical reactivity of the complexes with a series of organic ligands was investigated by time-resolved (step-scan) Fourier transform infrared (FTIR) spectroscopy. Interestingly, the photoreactions in pyridine and acetonitrile are fully reversible with a slow dark reverse reaction back to the educt species over minutes and even hours, depending on the metal center and reagent. This reversible behavior is in contrast to the expected loss of one or several CO ligands known from related homoleptic as well as heteroleptic M(CO)4L2 α-diimine transition-metal complexes.Fil: Bens, Tobias. Universitat Stuttgart; AlemaniaFil: Boden, Pit. Freie Universität Berlin; AlemaniaFil: Di Martino-Fumo, Patrick. Freie Universität Berlin; AlemaniaFil: Beerhues, Julia. Universitat Stuttgart; AlemaniaFil: Albold, Uta. Freie Universität Berlin; AlemaniaFil: Sobottka, Sebastian. Universitat Stuttgart; AlemaniaFil: Neuman, Nicolás Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Gerhards, Markus. Freie Universität Berlin; AlemaniaFil: Sarkar, Biprajit. Universitat Stuttgart; Alemani

Isomerization reactions in anionic mesoionic carbene-borates and control of properties and reactivities in the resulting coII complexes through agostic interactions

We present herein anionic borate-based bi-mesoionic carbene compounds of the 1,2,3-triazol-4-ylidene type that undergo C−N isomerization reactions. The isomerized compounds are excellent ligands for Co II centers. Strong agostic interactions with the “C−H”-groups of the cyclohexyl substituents result in an unusual low-spin square planar Co II complex, which is unreactive towards external substrates. Such agostic interactions are absent in the complex with phenyl substituents on the borate backbone. This complex displays a high-spin tetrahedral Co II center, which is reactive towards external substrates including dioxygen. To the best of our knowledge, this is also the first investigation of agostic interactions through single-crystal EPR spectroscopy. We conclusively show here that the structure and properties of these Co II complexes can be strongly influenced through interactions in the secondary coordination sphere. Additionally, we unravel a unique ligand rearrangement for these classes of anionic mesoionic carbene-based ligands

Rhodium diamidobenzene complexes: a tale of different substituents on the diamidobenzene ligand

Diamidobenzene ligands are a prominent class of redox-active ligands owing to their electron reservoir behaviour, as well as the possibility of tuning the steric and the electronic properties of such ligands through the substituents on the N-atoms of the ligands. In this contribution, we present Rh(III) complexes with four differently substituted diamidobenzene ligands. By using a combination of crystallography, NMR spectroscopy, electrochemistry, UV-vis-NIR/EPR spectroelectrochemistry, and quantum chemical calculations we show that the substituents on the ligands have a profound influence on the bonding, donor, electrochemical and spectroscopic properties of the Rh complexes. We present, for the first time, design strategies for the isolation of mononuclear Rh(II) metallates whose redox potentials span across more than 850 mV. These Rh(II) metallates undergo typical metalloradical reactivity such as activation of O2 and C–Cl bond activations. Additionally, we also show that the substituents on the ligands dictate the one versus two electron nature of the oxidation steps of the Rh complexes. Furthermore, the oxidative reactivity of the metal complexes with a [CH3]+ source leads to the isolation of a unprecedented, homobimetallic, heterovalent complex featuring a novel π-bonded rhodio-o-diiminoquionone. Our results thus reveal several new potentials of the diamidobenzene ligand class in organometallic reactivity and small molecule activation with potential relevance for catalysis

A dicopper( i )-dimesoionic carbene complex as a click catalyst: mechanistic implications

International audienceA dicopper(I) complex comprising a dimesoionic carbene and an acetate-bridge is synthesized and fully characterized. This complex is a potent pre-catalyst for the azide–alkyne cycloaddition reaction. A full kinetic investigation shows a first order in azide and a catalyst order smaller than one due to an equilibrated dimerization of the catalyst

Mono- and Di-Mesoionic Carbene-Boranes: Synthesis, Structures and Utility as Reducing Agents

Mesoionic carbenes (MIC) of the 1,2,3-triazol-5-ylidene type are currently popular ligands in organometallic chemistry. Their use in main group chemistry has been rather limited. In this contribution we present mono- and di-MIC-boranes with MICs based on triazolylidenes. The synthesis involves in-situ deprotonation of the corresponding triazolium salts and their reaction with boranes to form the desired compounds. Whereas this reaction route worked well for all triazolium salts derived from the 1,4-regioisomer of the triazoles, for the methlyene-bridged bi-triazolium salt derived from a 1,5-substiuted triazole, we observed the unexpected decomposition of the bi-triazolium and the formation of a triazole-borane with a new N−B bond. All compounds were characterized via multinuclear NMR spectroscopy, mass spectrometry, and single crystal X-ray diffraction. Furthermore, the MIC-boranes were used as reducing agents for the reduction of the C=O of aldehydes to the corresponding alcohols

The transformations of a methylene-bridged bis-triazolium salt: a mesoionic carbene based metallocage and analogues of TCNE and NacNac

Unusual and unexpected chemical transformations often provide access to completely new types of functional molecules. We report here the synthesis of a methylene-bridged bis-triazolium salt designed as a precursor for a new bis-mesoionic carbene (MIC) ligand. The direct metalation with silver oxide led to the isolation and crystallographic characterization of a cationic tetranuclear octacarbene-silver(i) complex. During metalation the formal bis-MIC precursor undergoes significant structural changes and chemical transformations. A combined synthetic, crystallographic and (spectro-)electrochemical approach is used to elucidate the mechanistic pathway: starting from the methylene-bridged bis-triazolium salt a single deprotonation leads to a NacNac analogue, which is followed by a redox-induced radical dimerization reaction, generating a new tetra-MIC ligand coordinated to silver(i) central atoms. Decomplexation led to the isolation of the corresponding tetratriazoliumethylene, a profoundly electron-poor alkene, which is an analogue of TCNE