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The intrinsic relationship between spin states and reactivity in peroxocobalt(III) complexes was investigated, specifically focusing on the influence of steric modulation on supporting ligands. Together with the previously reported [CoIII(TBDAP)(O2)]+ (2Tb), which exhibits spin crossover characteristics, two peroxocobalt(III) complexes, [CoIII(MDAP)(O2)]+ (2Me) and [CoIII(ADDAP)(O2)]+ (2Ad), bearing pyridinophane ligands with distinct N-substituents such as methyl and adamantyl groups, were synthesized and characterized. By manipulating the steric bulkiness of the N-substituents, control of spin states in peroxocobalt(III) complexes was demonstrated through various physicochemical analyses. Notably, 2Ad oxidized the nitriles to generate hydroximatocobalt(III) complexes, while 2Me displayed an inability for such oxidation reactions. Furthermore, both 2Ad and 2Tb exhibited similarities in spectroscopic and geometric features, demonstrating spin crossover behavior between S = 0 and S = 1. The steric bulkiness of the adamantyl and tert-butyl group on the axial amines was attributed to inducing a weak ligand field on the cobalt(III) center. Thus, 2Ad and 2Tb are an S = 1 state under the reaction conditions. In contrast, the less bulky methyl group on the amines of 2Me resulted in an S = 0 state. The redox potential of the peroxocobalt(III) complexes was also influenced by the ligand field arising from the steric bulkiness of the N-substituents in the order of 2Me (-0.01 V) < 2Tb (0.29 V) = 2Ad (0.29 V). Theoretical calculations using DFT supported the experimental observations, providing insights into the electronic structure and emphasizing the importance of the spin state of peroxocobalt(III) complexes in nitrile activation.
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The forward design of in vitro enzymatic reaction networks (ERNs) requires a detailed analysis of network kinetics and potentially hidden interactions between the substrates and enzymes. Although flow chemistry allows for a systematic exploration of how the networks adapt to continuously changing conditions, the analysis of the reaction products is often a bottleneck. Here, we report on the interface between a continuous stirred-tank reactor, in which an immobilized enzymatic network made of 12 enzymes is compartmentalized, and an ion mobility-mass spectrometer. Feeding uniformly 13C-labeled inputs to the enzymatic network generates all isotopically labeled reaction intermediates and products, which are individually detected by ion mobility-mass spectrometry (IMS-MS) based on their mass-to-charge ratios and inverse ion mobilities. The metabolic flux can be continuously and quantitatively monitored by diluting the ERN output with nonlabeled standards of known concentrations. The real-time quantitative data obtained by IMS-MS are then harnessed to train a model of network kinetics, which proves sufficiently predictive to control the ERN output after a single optimally designed experiment. The high resolution of the time-course data provided by this approach is an important stepping stone to design and control sizable and intricate ERNs.
Asunto(s)
Enzimas Inmovilizadas , Espectrometría de Masas , Espectrometría de Masas/métodos , Enzimas Inmovilizadas/química , Enzimas Inmovilizadas/metabolismo , Cinética , Espectrometría de Movilidad Iónica/métodosRESUMEN
Developing new enantioselective reactions is an important part of chemical discovery but requires time and resources to test large arrays of potential reaction conditions. New techniques are required to analyse many different reactions quickly and efficiently. Mass spectrometry is a high-throughput method; when combined with ion-mobility spectrometry, this technique can monitor diastereomeric reaction intermediates and thus be a handle to study enantioselective reactions. Through this technique and others, it was noted before that in the organocatalytic 1,4-addition to α,ß-unsaturated aldehydes, the abundance of initial diastereomeric intermediates correlates strongly to that of the final enantiomeric products. This work determines isomeric abundance for various catalysts and aldehydes and uses it to predict the enantiomeric excess of two control reactions. The prediction matches well for one reaction but does not predict the obtained results for the second. This finding confirms that the E/Z ratio of the iminium intermediates can be used as a predictor for some reactions, but the kinetics of the following steps can dramatically change the true enantioselectivity.
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Electrochemical steps are increasingly attractive for green chemistry. Understanding reactions at the electrode-solution interface, governed by kinetics and mass transport, is crucial. Traditional insights into these mechanisms are limited, but our study bridges this gap through an integrated approach combining voltammetry, electrochemical impedance spectroscopy, and electrospray ionization mass spectrometry. This technique offers real-time monitoring of the chemical processes at the electrode-solution interface, tracking changes in intermediates and products during reactions. Applied to the electrochemical reduction of oxygen catalyzed by the iron(II) tetraphenyl porphyrin complex, it successfully reveals various reaction intermediates and degradation pathways under different kinetic regimes. Our findings illuminate complex electrocatalytic processes and propose new ways for studying reactions in alternating current and voltage-pulse electrosynthesis. This advancement enhances our capacity to optimize electrochemical reactions for more sustainable chemical processes.
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Palladium-catalyzed carbonylation is a versatile method for the synthesis of various aldehydes, esters, lactones, or lactams. Alkoxycarbonylation of alkenes with carbon monoxide and alcohol produces either saturated or unsaturated esters as a result of two distinct catalytic cycles. The existing literature presents an inconsistent account of the procedures favoring oxidative carbonylation products. In this study, we have monitored the intermediates featured in both catalytic cycles of the methoxycarbonylation of styrene PhCH=CH2 as a model substrate, including all short-lived intermediates, using mass spectrometry. Comparing the reaction kinetics of the intermediates in both cycles in the same reaction mixture shows that the reaction proceeding via alkoxy intermediate [PdII]-OR, which gives rise to the unsaturated product PhCH=CHCO2Me, is faster. However, with an advancing reaction time, the gradually changing reaction conditions begin to favor the catalytic cycle dominated by palladium hydride [PdII]-H and alkyl intermediates, affording the saturated products PhCH2CH2CO2Me and PhCH(CO2Me)CH3 preferentially. The role of the oxidant proved to be crucial: using p-benzoquinone results in a gradual decrease of the pH during the reaction, swaying the system from oxidative conditions toward the palladium hydride cycle. By contrast, copper(II) acetate as an oxidant guards the pH within the 5-7 range and facilitates the formation of the alkoxy palladium complex [PdII]-OR, which favors the oxidative reaction producing PhCH=CHCO2Me with high selectivity. Hence, it is the oxidant, rather than the catalyst, that controls the reaction outcome by a mechanistic switch. Unraveling these principles broadens the scope for developing alkoxycarbonylation reactions and their application in organic synthesis.
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Copper nitrenoids are key intermediates in copper-catalyzed direct C-H amination reactions. Further development of this important reaction relies on knowing the properties and reactivity of the nitrenoid intermediates. This work utilizes antenna ligands to form copper nitrenoid complexes and monitor the consecutive C-H amination reactions under well-defined single-molecule conditions in the gas phase. The [Cu(Lphoto)(Lazide)]+ precursors (Lphoto is a bidentate antenna ligand, and Lazide is an organic azide) were stored in an ion trap at 3.5â K and irradiated by visible light, which resulted in denitrogenation of the complex. Further irradiation of the copper nitrenoid led to the consecutive C-H amination of the antenna ligand. The nitrenoid complexes, as well as the products of the C-H amination, were characterized by helium tagging IRPD spectroscopy, and the mechanism was described by DFT calculations. This research demonstrates that the antenna ligands can be used to promote the denitrogenation of metal azides in the gas phase and also channel the internal energy to promote further reactivity, which opens a new way to study the reactivity of highly reactive species under well-defined conditions.
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The premise of most studies on the homogeneous electrocatalytic CO2 reduction reaction (CO2RR) is a good understanding of the reaction mechanisms. Yet, analyzing the reaction intermediates formed at the working electrode is challenging and not always attainable. Here, we present a new, general approach to studying the reaction intermediates applied for CO2RR catalyzed by a series of cobalt complexes. The cobalt complexes were based on the TPA-ligands (TPA = tris(2-pyridylmethyl)amine) modified by amino groups in the secondary coordination sphere. By combining the electrochemical experiments, electrochemistry-coupled electrospray ionization mass spectrometry, with density functional theory (DFT) calculations, we identify and spectroscopically characterize the key reaction intermediates in the CO2RR and the competing hydrogen-evolution reaction (HER). Additionally, the experiments revealed the rarely reported in situ changes in the secondary coordination sphere of the cobalt complexes by the CO2-initiated transformation of the amino substituents to carbamates. This launched an even faster alternative HER pathway. The interplay of three catalytic cycles, as derived from the experiments and supported by the DFT calculations, explains the trends that cobalt complexes exhibit during the CO2RR and HER. Additionally, this study demonstrates the need for a molecular perspective in the electrocatalytic activation of small molecules efficiently obtained by the EC-ESI-MS technique.
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Photocatalytic reactions involving a reductive radical-polar crossover (RRPCO) generate intermediates with carbanionic reactivity. Many of these proposed intermediates resemble highly reactive organometallic compounds. However, conditions of their formation are generally not tolerated by their isolated organometallic versions and often a different reactivity is observed. Our investigations on their nature and reactivity under commonly used photocatalytic conditions demonstrate that these intermediates are indeed best described as free, superbasic carbanions capable of deprotonating common polar solvents usually assumed to be inert such as acetonitrile, dimethylformamide, and dimethylsulfoxide. Their basicity not only towards solvents but also towards electrophiles, such as aldehydes, ketones, and esters, is comparable to the reactivity of isolated carbanions in the gas-phase. Previously unsuccessful transformations thought to result from a lack of reactivity are explained by their high reactivity towards the solvent and weakly acidic protons of reaction partners. An intuitive explanation for the mode of action of photocatalytically generated carbanions is provided, which enables methods to verify reaction mechanisms proposed to involve an RRPCO step and to identify the reasons for the limitations of current methods.
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The Eschenmoser coupling reaction (ECR) of thioamides with electrophiles is believed to proceed via thiirane intermediates. However, little is known about converting the intermediates into ECR products. Previous mechanistic studies involved external thiophiles to remove the sulfur atom from the intermediates. In this work, an ECR proceeding without any thiophilic agent or base is studied by electrospray ionization-mass spectrometry. ESI-MS enables the detection of the so-far elusive polysulfide species Sn , with n ranging from 2 to 16 sulfur atoms, proposed to be the key species leading to product formation. Integrating observations from ion mobility spectrometry, ion spectroscopy, and reaction monitoring via flow chemistry coupled with mass spectrometry provides a comprehensive understanding of the reaction mechanism and uncovers the autocatalytic nature of the ECR reaction.
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Complex reaction mixtures, like those postulated on early Earth, present an analytical challenge because of the number of components, their similarity, and vastly different concentrations. Interpreting the reaction networks is typically based on simplified or partial data, limiting our insight. We present a new approach based on online monitoring of reaction mixtures formed by the formose reaction by ion-mobility-separation mass-spectrometry. Monitoring the reaction mixtures led to large data sets that we analyzed by non-negative matrix factorization, thereby identifying ion-signal groups capturing the time evolution of the network. The groups comprised ≈300 major ion signals corresponding to sugar-calcium complexes formed during the formose reaction. Multivariate analysis of the kinetic profiles of these complexes provided an overview of the interconnected kinetic processes in the solution, highlighting different pathways for sugar growth and the effects of different initiators on the initial kinetics. Reconstructing the network's topology further, we revealed so far unnoticed fast retro-aldol reaction of ketoses, which significantly affects the initial reaction dynamics. We also detected the onset of sugar-backbone branching for C6 â sugars and cyclization reactions starting for C5 â sugars. This top-down analytical approach opens a new way to analyze complex dynamic mixtures online with unprecedented coverage and time resolution.
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Metal hydride complexes are essential intermediates in hydrogenation reactions. The hydride-donor ability determines the scope of use of these complexes. We present a new, simple mass-spectrometry method to study the hydride-donor ability of metal hydrides using a series of 18 iron, cobalt, and nickel complexes with N- and P-based ligands (L). The mixing of [(L)MII(OTf)2] with NaBH4 forms [(L)MII(BH4)]+ (M = Fe, Co, Ni) that can be detected by electrospray ionization mass spectrometry. Energy-resolved collision-induced dissociations of [(L)MII(BH4)]+ provide threshold energies (ΔECID) for the formations of [(L)MII(H)]+ that correlate well with the hydride donor ability of the metal hydride complexes. We studied the vibrational and electronic spectra of the generated metal hydrides, assigned their structure and spin state, and demonstrated a good correlation between ΔECID and the M-H stretching vibration frequencies. The ΔECID also correlates with reaction rates for hydride transfer reactivity in the gas phase and known reactivity trends in the solution phase.
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The kinetic enantio-recognition of chiral viologen guests by planar-chiral porphyrin cage compounds, measured in terms of ΔΔGon, is determined by the planar-chirality of the host and influenced by the size, as measured by ion mobility-mass spectrometry, but not the chirality of its substituents.
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We report the synthesis and characterization of a mononuclear nonheme cobalt(III)-imidyl complex, [Co(NTs)(TQA)(OTf)]+ (1), with an S = 3/2 spin state that is capable of facilitating exogenous substrate modifications. Complex 1 was generated from the reaction of CoII(TQA)(OTf)2 with PhINTs at -20 °C. A flow setup with ESI-MS detection was used to explore the kinetics of the formation, stability, and degradation pathway of 1 in solution by treating the Co(II) precursor with PhINTs. Co K-edge XAS data revealed a distinct shift in the Co K-edge compared to the Co(II) precursor, in agreement with the formation of a Co(III) intermediate. The unusual S = 3/2 spin state was proposed based on EPR, DFT, and CASSCF calculations and Co Kß XES results. Co K-edge XAS and IR photodissociation (IRPD) spectroscopies demonstrate that 1 is a six-coordinate species, and IRPD and resonance Raman spectroscopies are consistent with 1 being exclusively the isomer with the NT ligand occupying the vacant site trans to the TQA aliphatic amine nitrogen atom. Electronic structure calculations (broken symmetry DFT and CASSCF/NEVPT2) demonstrate an S = 3/2 oxidation state resulting from the strong antiferromagnetic coupling of an â¢NTs spin to the high-spin S = 2 Co(III) center. Reactivity studies of 1 with PPh3 derivatives revealed its electrophilic characteristic in the nitrene-transfer reaction. While the activation of C-H bonds by 1 was proved to be kinetically challenging, 1 could oxidize weak O-H and N-H bonds. Complex 1 is, therefore, a rare example of a Co(III)-imidyl complex capable of exogenous substrate transformations.
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Complex speciation and exchange kinetics of labile ligands are critical parameters for understanding the reactivity of metal complexes in solution. We present a novel approach to determine ligand exchange parameters based on electrospray ionization mass spectrometry (ESI-MS). The introduction of isotopically labelled ligands to a solution of metal host and unlabelled ligands allows the quantitative investigation of the solution-phase equilibria. Furthermore, ion mobility separation can target individual isomers, such as ligands bound at specific sites. As a proof of concept, we investigate the solution equilibria of labile pyridine ligands coordinated in the cavity of macrocyclic porphyrin cage complexes bearing diamagnetic or paramagnetic metal centres. The effects of solvent, porphyrin coordination sphere, transition metal, and counterion on ligand dissociation are discussed. Rate constants and activation parameters for ligand dissociation in the solution can be derived from our ESI-MS approach, thereby providing mechanistic insights that are not easily obtained from traditional solution-phase techniques.
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Pd-catalyzed C-H functionalization reactions of non-directed substrates have recently emerged as an attractive alternative to the use of directing groups. Key to the success of these transformations has been the discovery of new ligands capable of increasing both the reactivity of the inert C-H bond and the selectivity of the process. Among them, a new type of S,O-ligand has been shown to be highly efficient in promoting a variety of Pd-catalyzed C-H olefination reactions of non-directed arenes. Despite the success of this type of S,O-ligand, its role in the C-H functionalization processes is unknown. Herein, we describe a detailed mechanistic study focused on elucidating the role of the S,O-ligand in the Pd-catalyzed C-H olefination of non-directed arenes. For this purpose, several mechanistic tools, including isolation and characterization of reactive intermediates, NMR and kinetic studies, isotope effects and DFT calculations have been employed. The data from these experiments suggest that the C-H activation is the rate-determining step in both cases with and without the S,O-ligand. Furthermore, the results indicate that the S,O-ligand triggers the formation of more reactive Pd cationic species, which explains the observed acceleration of the reaction. Together, these studies shed light on the role of the S,O-ligand in promoting Pd-catalyzed C-H functionalization reactions.
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Gold(I) centers can form moderately strong (Auâ â â H) hydrogen bonds with tertiary ammonium groups, as has been demonstrated in the 3AuCl+ (3+ =1-(tert-butyl)-3-phenyl-4-(2-((dimethylammonio)methyl)phenyl)-1,2,4-triazol-5-ylidene) complex. However, similar hydrogen bonding interactions with isoelectronic silver(I) or copper(I) centers are unknown. Herein, we first explored whether the Auâ â â H bond originally observed in 3AuCl+ can be strengthened by replacing Cl with Br or I. Experimental gas-phase IR spectra in the â¼3000â cm-1 region showed only a small effect of the halogen on the Auâ â â H bond. Next, we measured the spectra of 3AgCl+ , which exhibited significant differences compared to its 3AuX+ counterparts. The difference has been explained by DFT calculations which indicated that the Agâ â â H interaction is only marginal in this complex, and a Clâ â â H hydrogen bond is formed instead. Calculations predicted the same for the 3CuCl+ complex. However, we noticed that for Ag and Cu complexes with less flexible ligands, such as dimethyl(2-(dimethylammonio)phenyl)phosphine (L7 H+ ), the computations predict the presence of the respective Agâ â â H and Cuâ â â H hydrogen bonds, with a strength similar to the Auâ â â H bond in 3AuCl+ . We, therefore, propose possible complexes where the presence of (Ag/Cu)â â â H bonds could be experimentally verified to broaden our understanding of these unusual interactions.
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Cobalt(III)peroxo complexes serve as model metal complexes mediating oxygen activation. We report a systematic study of the effect of hydrogen bonding on the O2 binding energy and the O-O bond activation within the cobalt(III)peroxo complexes. To this end, we prepared a series of tris(pyridin-2-ylmethyl)amine-based cobalt(III)peroxo complexes having either none, one, two, or three amino groups in the secondary coordination sphere. The hydrogen bonding between the amino group(s) and the peroxo ligand was investigated within the isolated complexes in the gas phase using helium tagging infrared photodissociation spectroscopy, energy-resolved collision-induced dissociation experiments, and density functional theory. The results show that the hydrogen bonding stabilizes the cobalt(III)peroxo core, but the effect is only 10-20 kJ mol-1. Introducing the first amino group to the secondary coordination sphere has the largest stabilization effect; more amino groups do not change the results significantly. The amino group can transfer a hydrogen atom to the peroxo ligands, which results in the O-O bond cleavage. This process is thermodynamically favored over the O2 elimination but entropically disfavored.
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The strong C-H bond activation of hydrocarbons is a difficult reaction in environmental and biological chemistry. Herein, a high-valent manganese(IV)-hydroxo complex, [MnIV(CHDAP-O)(OH)]2+ (2), was synthesized and characterized by various physicochemical measurements, such as ultraviolet-visible (UV-vis), electrospray ionization-mass spectrometry (ESI-MS), electron paramagnetic resonance (EPR), and helium-tagging infrared photodissociation (IRPD) methods. The one-electron reduction potential (Ered) of 2 was determined to be 0.93 V vs SCE by redox titration. 2 is formed via a transient green species assigned to a manganese(IV)-bis(hydroxo) complex, [MnIV(CHDAP)(OH)2]2+ (2'), which performs intramolecular aliphatic C-H bond activation. The kinetic isotope effect (KIE) value of 4.8 in the intramolecular oxidation was observed, which indicates that the C-H bond activation occurs via rate-determining hydrogen atom abstraction. Further, complex 2 can activate the C-H bonds of aromatic compounds, anthracene and its derivatives, under mild conditions. The KIE value of 1.0 was obtained in the oxidation of anthracene. The rate constant (ket) of electron transfer (ET) from N,N'-dimethylaniline derivatives to 2 is fitted by Marcus theory of electron transfer to afford the reorganization energy of ET (λ = 1.59 eV). The driving force dependence of log ket for oxidation of anthracene derivatives by 2 is well evaluated by Marcus theory of electron transfer. Detailed kinetic studies, including the KIE value and Marcus theory of outer-sphere electron transfer, imply that the mechanism of aromatic C-H bond hydroxylation by 2 proceeds via the rate-determining electron-transfer pathway.
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Hidrógeno , Manganeso , Manganeso/química , Cinética , Oxidación-Reducción , Hidrógeno/química , AntracenosRESUMEN
Macrocyclic metal porphyrin complexes can act as shape-selective catalysts mimicking the action of enzymes. To achieve enzyme-like reactivity, a mechanistic understanding of the reaction at the molecular level is needed. We report a mechanistic study of alkene epoxidation by the oxidant iodosylbenzene, mediated by an achiral and a chiral manganese(V)oxo porphyrin cage complex. Both complexes convert a great variety of alkenes into epoxides in yields varying between 20-88 %. We monitored the process of the formation of the manganese(V)oxo complexes by oxygen transfer from iodosylbenzene to manganese(III) complexes and their reactivity by ion mobility mass spectrometry. The results show that in the case of the achiral cage complex the initial iodosylbenzene adduct is formed on the inside of the cage and in the case of the chiral one on the outside of the cage. Its decomposition leads to a manganese complex with the oxo ligand on either the inside or outside of the cage. These experimental results are confirmed by DFT calculations. The oxo ligand on the outside of the cage reacts faster with a substrate molecule than the oxo ligand on the inside. The results indicate how the catalytic activity of the macrocyclic porphyrin complex can be tuned and explain why the chiral porphyrin complex does not catalyze the enantioselective epoxidation of alkenes.
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Gold(II) complexes are rare, and their application to the catalysis of chemical transformations is underexplored. The reason is their easy oxidation or reduction to more stable gold(III) or gold(I) complexes, respectively. We explored the thermodynamics of the formation of [AuII (L)(X)]+ complexes (L=ligand, X=halogen) from the corresponding gold(III) precursors and investigated their stability and spectral properties in the IR and visible range in the gas phase. The results show that the best ancillary ligands L for stabilizing gaseous [AuII (L)(X)]+ complexes are bidentate and tridentate ligands with nitrogen donor atoms. The electronic structure and spectral properties of the investigated gold(II) complexes were correlated with quantum chemical calculations. The results show that the molecular and electronic structure of the gold(II) complexes as well as their spectroscopic properties are very similar to those of analogous stable copper(II) complexes.