Liquid Dynamics Determine Transition Metal‐<i>N</i>‐Heterocyclic Carbene Complex Formation

Zaby, Paul; Müller, Anna K; Blasius, Jan; Nolan, Steven P.; Hollóczki, Oldamur

doi:10.1002/chem.202203636

Cited by 8 publications

(7 citation statements)

References 92 publications

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“…The presented solution-phase enthalpies were obtained using an implicit continuum solvation model, thus not including explicit solvation. This approach usually delivers reliable results and serves as a good approximation for solution-phase systems, although it could be the root of some inaccuracies in the calculated barriers. − …”

Section: Resultsmentioning

confidence: 99%

Stronger Together! Mechanistic Investigation into Synergistic Effects during Homogeneous Carbon Dioxide Hydrogenation Using a Heterobimetallic Catalyst

Fickenscher

Lönnecke

Müller³

et al. 2023

Inorg. Chem.

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A series of group 6 heterobimetallic complexes [M0;IrIII] (M = Cr, Mo, W) were synthesized and fully characterized, and the catalytic behavior was studied. The heterobimetallic complex [Mo0;IrIII] (C1) was by far the most active and has shown a considerable synergistic effect, with both metals actively participating in homogeneous carbon dioxide hydrogenation, leading to formate salts. Based on theoretical calculations, the synergistic interaction is due to Pauli repulsion, lowering the transition state and thus enabling higher catalytic activity. The mechanism of both the hydrogenation itself and the synergistic interaction was studied by NMR spectroscopy, kinetic measurements, and theoretical calculations. The homogeneous nature of the reaction was proven using in situ high-pressure (HP) NMR experiments. The same experiments also showed that the octahedral Mo(CO)3P3 moiety of the complex is stable under the reaction conditions. The hydride complex is the resting state because the hydride transfer is the rate-determining step. This is supported by kinetic measurements, in situ HP NMR experiments, and theoretical calculations and is in contrast to the monometallic IrIII counterpart of C1.

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Section: Resultsmentioning

confidence: 99%

Stronger Together! Mechanistic Investigation into Synergistic Effects during Homogeneous Carbon Dioxide Hydrogenation Using a Heterobimetallic Catalyst

Fickenscher

Lönnecke

Müller³

et al. 2023

Inorg. Chem.

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“…The critical and specific role played by chloride anions in the hydrolysis process could, however, be more likely the consequence of strong, long‐range ion‐ion interactions with the base, as recently evidenced by Hollóczki et al . in molecular dynamics simulation experiments [17] …”

Section: Resultsmentioning

confidence: 99%

The Facile Hydrolysis of Imidazolinium Chlorides (N‐Heterocyclic Carbene Precursors) Under Basic Aqueous Conditions

Touj,

Taping,

Tumanov

et al. 2023

Chemistry A European J

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The hydrolysis of imidazolinium chlorides takes place readily in a basic water/dichloromethane biphasic mixture at room temperature. Experimental parameters were optimized to afford full conversions and high yields of γ‐aminoformamides starting from twelve symmetrical substrates with alkyl or aryl substituents on their nitrogen atoms, and five unsymmetrical 1‐alkyl‐3‐arylimidazolinium chlorides. NMR and XRD analyses showed that the cleavage of unsymmetrical salts led to γ‐alkylamino‐N‐arylformamides with a high regioselectivity and that bulky alkyl or aryl groups on the formamide moiety led to the isolation of the (E)‐isomer in high stereoisomeric purity (>95 %), whereas smaller and more flexible alkyl substituents afforded mixtures of (E)‐ and (Z)‐rotamers. Control experiments showed that the hydrolysis of 1,3‐dimesitylimidazolinium chloride (SIMes ⋅ HCl) did not occur readily in pure or acidic water and that the presence of bulky aromatic substituents on the nitrogen atoms of 1,3‐bis(2,6‐diisopropylphenyl)imidazolinium chloride (SIDip ⋅ HCl) efficiently slowed down its hydrolysis under basic aqueous conditions. Most strikingly, this work highlighted the critical influence of the counteranion on the reactivity of imidazolinium cations. Indeed, the chloride salts underwent a facile hydrolysis in the presence of water and Na2CO3, whereas various other NHC ⋅ HX derivatives reacted much slower or remained essentially inert under these conditions.

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“…Future research must build upon the current understanding with regards to the superiority of inorganic bases as a result of ion association in solution and not as an exclusive matter of base strength. These challenges lie in intensifying and generalizing the application of the weak base route in the metalation of more types of azolium salts with various metal sources. , Despite the recent advances with CAACs and mesoionic carbenes of the 1,2,3-triazolylidene type, which are more donating than imidazol(in)ylidenes and the corresponding azolium salts are less C–H acidic, , there are many opportunities to develop general conditions and to understand the effects of various components on the metalation step (i.e., the counteranion of the azolium salt, the metal source, the exact composition of the base). Finally, combining metal-NHC synthesis with subsequent functionalization to construct complexes that are ready to be utilized in synthetic, (photo)catalytic, or medicinal applications in a single synthetic operation is still an underexplored direction.…”

Section: Discussionmentioning

confidence: 99%

Advances in the Synthesis and Applications of N-Heterocyclic Carbene Metal Complexes with a Focus on the Weak Base Route

Scattolin,

Logvinov,

Tzouras

et al. 2023

Organometallics

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N-heterocyclic carbene (NHC) ligands have evolved from being simple lab curiosities to tertiary phosphine mimics to finally take center stage as unique supporting ligands in organometallic chemistry, homogeneous catalysis, and more recently in medicinal chemistry and materials science applications. Some of these aspects are presented here from a perspective of researchers that have been fascinated by the area for quite some time.

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Liquid Dynamics Determine Transition Metal‐N‐Heterocyclic Carbene Complex Formation

Cited by 8 publications

References 92 publications

Stronger Together! Mechanistic Investigation into Synergistic Effects during Homogeneous Carbon Dioxide Hydrogenation Using a Heterobimetallic Catalyst

Stronger Together! Mechanistic Investigation into Synergistic Effects during Homogeneous Carbon Dioxide Hydrogenation Using a Heterobimetallic Catalyst

The Facile Hydrolysis of Imidazolinium Chlorides (N‐Heterocyclic Carbene Precursors) Under Basic Aqueous Conditions

Advances in the Synthesis and Applications of N-Heterocyclic Carbene Metal Complexes with a Focus on the Weak Base Route

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