Homogeneously catalyzed reactions often make use of additives and promotors that affect reactivity patterns and improve catalytic performance. While the role of reaction promotors is often discussed in view of their chemical reactivity, we demonstrate that they can be involved in catalysis indirectly. In particular, we demonstrate that promotors can adjust the thermodynamics of key transformations in homogeneous hydrogenation catalysis and enable reactions that would be unfavorable otherwise. We identified this phenomenon in a set of well-established and new Mn pincer catalysts that suffer from persistent product inhibition in ester hydrogenation. Although alkoxide base additives do not directly participate in inhibitory transformations, they can affect the equilibrium constants of these processes. Experimentally, we confirm that by varying the base promotor concentration one can control catalyst speciation and inflict substantial changes to the standard free energies of the key steps in the catalytic cycle. Despite the fact that the latter are universally assumed to be constant, we demonstrate that reaction thermodynamics and catalyst state are subject to external control. These results suggest that reaction promotors can be viewed as an integral component of the reaction medium, on its own capable of improving the catalytic performance and reshaping the seemingly rigid thermodynamic landscape of the catalytic transformation.

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Activation of homogeneous catalysts is an important step in ensuring efficient operation of any catalytic system as a whole. For the majority of pincer catalysts, the activation step leans heavily on the metal ligand cooperative chemistry that allows these complexes to react with small molecule substrates and engage in catalytic transformations. While the majority of such catalysts require a single activation event to become cooperative, herein we report an exception to this trend. Specifically, we demonstrate that a Ru-PN³P aminopyridine pincer catalyst, which lacks conventional reactivity with hydrogen upon typical one-fold activation, can exhibit this reactivity when a sequential two-step activation is performed. The resulting anionic complexes readily activate molecular hydrogen and react further with CO₂ showing the previously unknown reactivity that is critical for CO₂ hydrogenation catalysts. While active in CO₂ hydrogenation, Ru-PN³Ps are significantly more efficient in hydrogenation of bicarbonates - a likely consequence of the chemistry of these pincers requiring formation of anionic complexes for hydrogen activation.

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Any catalyst should be efficient and stable to be implemented in practice. This requirement is particularly valid for manganese hydrogenation catalysts. While representing a more sustainable alternative to conventional noble metal-based systems, manganese hydrogenation catalysts are prone to degrade under catalytic conditions once operation temperatures are high. Herein, we report a highly efficient Mn(I)-CNP pre-catalyst which gives rise to the excellent productivity (TOF° up to 41 000 h⁻¹) and stability (TON up to 200 000) in hydrogenation catalysis. This system enables near-quantitative hydrogenation of ketones, imines, aldehydes and formate esters at the catalyst loadings as low as 5–200 p.p.m. Our analysis points to the crucial role of the catalyst activation step for the catalytic performance and stability of the system. While conventional activation employing alkoxide bases can ultimately provide catalytically competent species under hydrogen atmosphere, activation of Mn(I) pre-catalyst with hydride donor promoters, e.g. KHBEt₃, dramatically improves catalytic performance of the system and eliminates induction times associated with slow catalyst activation.

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Catalytic reductions of carbonyl-containing compounds are highly important for the safe, sustainable, and economical production of alcohols. Herein, we report on the efficient transfer hydrogenation of ketones catalyzed by a highly potent Mn(I)−NHC complex. Mn−NHC 1 is practical at metal concentrations as low as 75 ppm, thus approaching loadings more conventionally reserved for noble metal based systems. With these low Mn concentrations, catalyst deactivation is found to be highly temperature dependent and becomes especially prominent at increased reaction temperature. Ultimately, understanding of deactivation pathways could help close the activity/stability-gap with Ru and Ir catalysts towards the practical implementation of sustainable earth-abundant Mn-complexes.

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The catalytic asymmetric transfer hydrogenation (ATH) of ketones is a powerful methodology for the practical and efficient installation of chiral centers. Herein, we describe the synthesis, characterization, and catalytic application of a series of manganese complexes bearing simple chiral diamine ligands. We performed an extensive experimental and computational mechanistic study and present the first detailed experimental kinetic study of Mn-catalyzed ATH. We demonstrate that conventional mechanistic approaches toward catalyst optimization fail and how apparently different precatalysts lead to identical intermediates and thus catalytic performance. Ultimately, the Mn-N,N complexes under study enable quantitative ATH of acetophenones to the corresponding chiral alcohols with 75-87% ee.

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Photoluminescent compounds can undergo various structural changes upon interaction with light. When these changes manifest themselves in the excited state, the resulting emitters can obtain a sensory function. In this work, we designed coordination compounds that can vary their emission color in response to thermal and mechanical stimuli. When embedded in a polymer matrix, Cu-NHC sensors act as mechanophores, and their color-based response can readily describe mechanical stress and phase transition phenomena. A strong practical advantage of new mechanophores over previous generations of organometallic stress sensors stems from their reliance on emission color variations that are easy to detect. In a broad context, our work implies that emission color variations that we often view as thermally governed can also be triggered mechanically and used to generate sensory information.@en

Structural heterogeneity defines the properties of many functional polymers and it is often crucial for their performance and ability to withstand mechanical impact. Such heterogeneity, however, poses a tremendous challenge for characterization of these materials and limits our ability to design them rationally. Herein we present a practical methodology capable of resolving the complex mechanical behavior and tracking mechanical impact in discrete phases of segmented polyurethane—a typical example of a structurally complex polymer. Using direct optical imaging of photoluminescence produced by a small-molecule organometallic mechano-responsive sensor we observe in real time how polymer phases dissipate energy, restructure, and breakdown upon mechanical impact. Owing to its simplicity and robustness, this method has potential in describing the evolution of complex soft-matter systems for which global characterization techniques fall short of providing molecular-level insight.

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A series of substituted, pyridyl-functionalized 2,4,6-triarylpyrylium salts were prepared and investigated for their light absorption and emission properties. After reaction with P(SiMe₃)₃, the corresponding λ³-phosphinines were obtained, which carry on the 4- or 6-aryl ring ±I and ±M substituents. Supported by DFT calculations, a systematic evaluation of the σ-donor and π-donor as well as π-acceptor properties of these low-coordinate P,N-hybrid ligands was performed. The modular synthetic approach allowed us at the same time to synthesize the structurally related bipyridine derivatives for comparison reasons. Reaction of the chelating ligands with [W(CO)₆] in THF afforded the corresponding [(P^N)W(CO)₄] and [(N^N)W(CO)₄] complexes. A crystallographic characterization of selected coordination compounds revealed significant structural differences between the pyridyl-phosphinine- and the bipyridine-based compounds. Their characterization by means of IR-spectroscopy gave experimental insight into the electronic properties of the respective ligands.

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