Effects Of Ligands Research Articles

Rational Design of Ligand-immobilized Rh/IRMOFs Catalysts for 1-butene Hydroformylation with High Regioselectivity

The diverse pore structures and excellent tunable proprieties of IRMOFs materials made the possibility to explore the effect of the mode of ligand-immobilization on its catalytic performance for 1-butene hydroformylation. In this work, we report a successful case of theory-guided rational design of a highly active ligand-immobilized Rh/IRMOF catalyst based on previous work. Density functional theory calculations of elementary reaction barriers for 1-butene hydroformylation over 1Rh/IRMOFs-PPh3 models (IRMOF-1, -8, -10, -14, and -16) were performed. The calculation results and topographic steric maps analysis predicted that 1Rh/IRMOF-10-PPh3 have superior catalytic performance. This can be attributed to the “shape-selective” effect of phosphine ligands grafted in the backbone on the reactive transition state. In addition, the anchoring positions of the phenyl phosphine ligand grafting on the skeleton of 1Rh/IRMOF-10-PPh3 was identified in details. The 1Rh/IRMOF-10-PPh3[3-3] was predicted to have the highest n/i ratio. In order to verify the theoretical prediction, 1Rh/IRMOF-10-32PPh3 catalyst was prepared by post-synthesis strategy and the n/i ratio was experimentally confirmed to be 3.49, which outperform the previous 1Rh/MOF-5-PPh3 catalyst. This work suggests that the 1Rh/IRMOF-10-PPh3 catalyst can be a promising catalyst for hydroformylation reactions.

Substitution of the axial Type 1 Cu Ligand Afford Binding of a Water Molecule in Axial Position Affecting Kinetics, Spectral, and Structural Properties of the Small Laccase Ssl1.

Multicopper oxidases use Cu ions as cofactors to oxidize various substrates. High reduction potential at Type 1 Cu is considered as crucial for effective catalysis. Previous studies have shown that replacing the axial methionine ligand of the Type 1 Cu with leucine or phenylalanine leads to an increased reduction potential, but not always to higher enzyme activity. Here we present a study of six variants of the small laccase Ssl1 from Streptomyces sviceus, where the axial methionine ligand was substituted and the effect of the axial ligand on reduction potential, activity, spectral properties and structure was investigated. Absorption, electronic circular dichroism and EPR spectra revealed the presence of a stronger coordinating axial ligand like oxygen, which influences the electronic and catalytic properties more than the nature of the amino acid side chain. The crystal structures of the Ssl1 variants were solved, which show that none of the amino acids side chains coordinates to the Cu. Instead, a water molecule is found in the axial coordination site, which support the spectroscopic data. Our findings highlight the importance of combining structural and spectroscopic methods to investigate the effect of amino acid exchange on multicopper oxidases.

Tunable Blue-Light-Emitting Organic-Inorganic Zinc Halides with Thermally Activated Delayed Fluorescence and Room-Temperature Phosphorescence.

Hybrid metal halides have received great interests in the field of solid-state lighting technologies due to their diverse structures and excellent emission properties. In this work, we report the synthesis and characterization of four blue-emitting zero-dimensional hybrid metal halides, namely, (2HP)2ZnCl2, (2HP)2ZnBr2, (2TP)2ZnCl2, and (2TP)2ZnBr2 (2HP = 2-hydroxypyridine, 2TP = pyridine-2-thiol). By changing the ligands and halides, a remarkable increase in the photoluminescence quantum yield of (2HP)2ZnCl2 (44.7%) compared to (2TP)2ZnBr2 (1.8%) is realized. The 2HP series features excitation-dependent emission characteristics, whereas the 2TP series does not due to the effect of a different organic ligand. Utilizing time-resolved and temperature-dependent photoluminescence spectroscopies, all four compounds exhibit both thermally activated delayed fluorescence and room-temperature phosphorescence properties. These materials have excellent ambient and thermal stabilities and are solution-processable. Our work shows the importance of carefully incorporating organic ligands with the appropriate inorganic metal center to achieve tunable emission properties.

Predictive Models for Ligand Effects on a Reactive Al-Containing Radical Intermediate from Multivariate Linear Regression Analysis

Predictive Models for Ligand Effects on a Reactive Al-Containing Radical Intermediate from Multivariate Linear Regression Analysis

Anti-Inflammatory Effects of SGLT1 Synthetic Ligand in In Vitro and In Vivo Models of Lung Diseases

Background. Several research findings suggest that sodium–glucose co-transporter 1 (SGLT1) is implicated in the progression and control of infections and inflammation processes at the pulmonary level. Moreover, our previous works indicate an engagement of SGLT1 in inhibiting the inflammatory response induced in intestinal epithelial cells by TLR agonists. In this study, we report the anti-inflammatory effects observed in the lung upon engagement of the transporter, and upon the use of glucose and BLF501, a synthetic SGLT1 ligand, for the treatment of animal models of lung inflammation, including a model of allergic asthma. Methods. In vitro experiments were carried out on human pneumocytes stimulated with LPS from Pseudomonas aeruginosa and co-treated with glucose or BLF501, and the production of IL-8 was determined. The anti-inflammatory effect associated with SGLT1 engagement was then assessed in in vivo models of LPS-induced lung injury, as well as in a murine model of ovalbumin (OVA)-induced asthma, treating mice with aerosolized LPS and the synthetic ligand. After the treatments, lung samples were collected and analyzed for morphological alterations by histological examination and immunohistochemical analysis; serum and BALF samples were collected for the determination of several pro- and anti-inflammatory markers. Results. In vitro experiments on human pneumocytes treated with LPS showed significant inhibition of IL-8 production. The results of two in vivo experimental models, mice exposed to aerosolized LPS and OVA-induced asthma, revealed that the engagement of glucose transport protein 1 (SGLT1) induced a significant anti-inflammatory effect in the lungs. In the first model, the acute respiratory distress induced in mice was abrogated by co-treatment with the ligand, with almost complete recovery of the lung morphology and physiology. Similar results were observed in the OVA-induced model of allergic asthma, both with aerosolized and oral BLF501, suggesting an engagement of SGLT1 expressed both in intestinal and alveolar cells. Conclusions. Our results confirmed the engagement of SGLT1 in lung inflammation processes and suggested that BLF501, a non-metabolizable synthetic ligand of the co-transporter, might represent a drug candidate for therapeutic intervention against lung inflammation states.

Molecular properties of a triazole–Ce(III) complex with antioxidant activity: structure, spectroscopy, and relationships with related derivatives. Influence of the ligands in the complex

A novel Ce(III) complex with the triazole ligand 2b, which presents four H-bonded sites with amino acids of the MMP-2 receptor, was synthesized. The experimental IR and Raman spectra of this Ce(III) complex were well-interpreted based on their comparison to the theoretical scaled spectra using the scaling equations determined by two procedures and four density functional theory (DFT) levels. Therefore, the structure predicted for the synthesized Ce(III) complex was clearly characterized and confirmed. The potential antioxidant action of this complex was compared with the analogous La(III) complex, and it was found that the coordination of ligand 2b with Ce(III) improves the ligand’s ability to participate in single-electron transfer (SET), as observed in the ABTS·+ assay, and this complex seems to scavenge the stable radical much more actively compared to its La(III) counterpart. Additionally, interactions with potassium superoxide and sodium hypochlorite indicate a high pro-oxidant behavior of the complex. The effects of different ligands on the geometric parameters, atomic charges, and molecular properties of the Ce(III) complex were analyzed at four DFT levels, and several relationships were clearly established. These relationships can facilitate the selection of new ligands with improved properties in the design of novel lanthanide–triazole carboxylate complexes with promising biological activity. The ligand size increase in the complexes facilitates the electronic transfer of negative charge, and the low HOMO (highest occupied molecular orbital)–LUMO (lowest unoccupied molecular orbital) energy gap indicates a large reactivity and low energy for their excitation.

Elucidating the Interplay between Symmetry Distortions in Passivated MAPbI3 and the Rashba Splitting Effect.

Hybrid organic-inorganic perovskites play a critical role in modern optoelectronic applications, particularly as single photon sources due to their unusual bright ground state. However, the presence of trap states resulting from surface dangling bonds hinders their widespread commercial application. This work uses density functional theory (DFT) to study the effects of various passivating ligands and their binding sites on Rashba splitting, a phenomenon directly linked to the bright ground state. Our results predict that X2- and X4-type ligands that adsorb at acidic oxygen binding sites and zwitterionic binding sites efficiently eliminate trap states introduced by surface iodine vacancies. Furthermore, our results show that distortions from the nominally symmetric cubic structure of the perovskite predominantly determine the presence and magnitude of the Rashba splitting. Specifically, the loss of more symmetry elements consistently leads to Rashba splitting in both the valence band (VB) and the conduction band (CB) with small Rashba splitting coefficients. Conversely, although inversion symmetry breaking alone fails to guarantee the presence of pure Rashba splitting in both the VB and the CB, it significantly increases the degree of splitting. The adsorption of ligands not only mitigates trap states but also plays a critical role in altering the local symmetry, thus influencing Rashba splitting. DFT predicts a distinct Rashba-Dresselhaus splitting in the CB with X2 ligands, causing the largest splitting. The presence of local electric fields causes consistent Rashba splitting of the VB across all studied systems except for the X4 zwitterionic passivated systems (sulfobetaine and lecithin). Electric fields are predicted to cause significant splitting of the CB, particularly for MAPbI3 and SH passivated MAPbI3 surfaces that possess freely rotating ligand binding sites. This study reveals that the wavelength, tunability of Rashba splitting through an applied electric field, and nature of Rashba-Dresselhaus splitting are influenced by the characteristics of the ligand binding site. On the other hand, pure Rashba splitting is predicted to exhibit a greater susceptibility to symmetry distortion than to specific ligand binding sites. These findings elucidate how surface passivating ligands and symmetry distortions influence Rashba splitting, shaping the optoelectronic properties of perovskite nanocrystals.

Atomically precise copper clusters with dual sites for highly chemoselective and efficient hydroboration.

The hydroboration of alkynes into vinylboronate esters is a vital transformation, but achieving high chemoselectivity of targeted functional groups and an appreciable turnover number is a considerable challenge. Herein, we develop two dynamically regulating dual-catalytic-site copper clusters (Cu4NC and Cu8NC) bearing N-heterocyclic thione ligands that endow Cu4NC and Cu8NC catalysts with performance. In particular, the performance of microcrystalline Cu4NC in hydroboration is characterized by a high turnover number (77786), a high chemoselectivity, high recovery and reusability under mild conditions. Mechanistic studies and density functional theory calculations reveal that, compared with the Cu8NC catalyst, the Cu4NC catalyst has a lower activation energy for hydroboration, accounting for its high catalytic activity. This work reveals that precisely constructed cluster catalysts with dual catalytic sites may provide a way to substantially improve catalytic properties by fully leveraging synergistic interactions and dynamic ligand effects, thus promoting the development of cluster catalysts.

Satellite Pd Single-Atom Embraced AuPd Alloy Nanoclusters for Enhanced Hydrogen Evolution.

The fabrication of hybrid active sites that synergistically contain nanoclusters and single atoms (SAs) is vital for electrocatalysts to achieve excellent activity and durability. Herein, we develop a ligand-assisted pyrolysis strategy using nanoclusters (Au4Pd2(SC2H4Ph)8) with alloy cores and protected ligands to build AuPd cluster sites embraced by satellite Pd SAs. In the thermal drive control process, different thermodynamic properties of the alloy atoms and the confinement effects of organic ligands allow for the mild spillover of the single-component metal Pd, resulting in the formation of AuPd alloy nanoclusters tightly encompassed by isolated Pd atoms. Experiments and theoretical calculations indicated that the satellite Pd atoms can optimize the electronic structure of the AuPd nanoclusters and Au sites in the alloy to facilitate the adsorption and dissociation of H2O, thus enhancing the hydrogen evolution reaction (HER) activity. The optimal AuPdNCs/PdSAs-600 exhibits outstanding electrocatalytic activity toward HER, with overpotentials of 21 and 38 mV at 10 mA cm-2 in acidic and alkaline media, respectively. Moreover, the mass activity and turnover frequency of AuPdNCs/PdSAs-600 are one order of magnitude higher than those of commercial Pd/C and Pt/C catalysts. This facile strategy for constructing hybrid catalytic centers using ligand-protected nanoclusters provides efficient insights for the further design of nanocluster-based electrocatalysts synergized by SAs.

Revealing the effects of functional group in organic linkers on properties of metal organic frameworks electrode and their performance in supercapacitors

The history of developing supercapacitors with increased performance is inextricably linked to the exploration and design of suitable electrode materials. Metal-organic frameworks (MOFs) have attracted intensive attention for use in high-performance supercapacitors thanks to their large specific surface area, tuneable pore sizes and crystal structure. Understanding the influence of MOF structures and properties on the performance of supercapacitors is critical to enhancing their performance. However, so far researchers have been keen on exploring metal atoms in MOFs and have ignored the effects of organic ligands, especially the functional groups thereon, on supercapacitors. In this work, we have studied the impact of organic linkers’ functional groups on the properties of MOFs and how this influences their performance as supercapacitor electrode materials. We synthesized four MOFs with different functional groups, including hydroxyl, nitride and thiol groups and characterised their physicochemical properties and their performance as supercapacitor electrode materials. Characterisation of the specific surface area shows that the BET area decreases from 980.3 m2 g−1 for the original MOF to 12.2 m2 g−1 when the thiol group is incorporated. Furthermore the –OH, –NH, and −SH functionalities reduced the charge transfer resistance (< 1 Ω) and induced more pseudocapacitance, whereas the –OH group dramatically increased the hydrophilicity of the electrode and rate performance of supercapacitors. Although the MOFs without extra function group showed the highest specific capacitance of 1495F g−1, analysis of the normalized areal specific capacitance only shows 1.5 F m−2. The MOFs with the −SH group showed the highest normalized areal specific capacitance of 26F m−2 as well as stable cycling performance of 80 % retention after 10,000 cycles.

Computational screening and investigation of ligand effect on TM single atom catalyst for hydrogen evolution reaction

Here, we studied the stability, electronic characteristics, and HER catalytic performance of a transition metal single atom catalysts, both with and without the presence of chlorine ligand. The findings indicate that all catalysts, except for Au, Au-Cl, Ag, Ag-Cl, are thermodynamically stable. We found 3d transition metals are more stable than those in the 4d and 5d series. Ag-Cl, Sc, Ag, Fe-Cl, and Cr-Cl have the poorest electrochemical stability. We found a negative Pearson correlation between Fermi energy and formation energy for TM-Cl, which is opposite to the trend observed for bare TM catalysts. The higher HER activity of chlorine bonded system for the early 3d TM suggests that the downshifting of the d-band center facilitates the activity. We also observed a periodic trend in the d-band center for both TM and TM-Cl systems. Mn-Cl, Cr-Cl, Ti-Cl, Fe-Cl, V-Cl and Zn emerged as the superior catalysts in our study series.

High Oxygen Reduction Efficiency and Durability of Nano-Honeycomb Pt3(NiFeCo) Replenished by High-Entropy Metallic Glass Support.

Developing low-Pt oxygen reduction reaction (ORR) catalysts with high efficiency and robustness is critical for practical fuel cells. The most advanced ORR catalysts either feature high percentages of Pt (>70 at.%) or exhibit poor durability when reducing Pt loading. Herein, a multicomponent solid-solution Pt3(FeCoNi) honeycomb nano-framework supported by the specially designed high-entropy metallic glass (MG) is reported for efficient ORR. This hybrid catalyst with a low surface Pt loading of 5.79µgcm-2 displays exceptional mass and specific activities of 7.02Amgpt -1 and 8.15mAcmPt -2 at 0.9V, respectively, which are ≈15 and 22 times higher compared with commercial Pt/C. The analyses reveal the weakened chemisorption of oxygenated species, which is induced by the strong strain and ligand effects originating from the synergistic multicomponent alloying. This in turn enhances the intrinsic ORR activity. Moreover, benefiting from a unique replenishment behavior, the hybrid catalyst delivers ultra-high durability with negligible activity decay even after 50 000 potential cycles. This mechanism is achieved by sacrificing the interior MG supplementary support to dynamically compensate for the loss of catalytically active surface. The work provides an alternative way to design more efficient and durable low-Pt electrocatalysts for electrochemical devices.

Harnessing the Synergistic Interplay between Atomic-Scale Vacancies and Ligand Effect to Optimize the Oxygen Reduction Activity and Tolerance Performance.

Defect engineering is an effective strategy for regulating the electrocatalysis of nanomaterials, yet it is seldom considered for modulating Pt-based electrocatalysts for the oxygen reduction reaction (ORR). In this study, we designed Ni-doped vacancy-rich Pt nanoparticles anchored on nitrogen-doped graphene (Vac-NiPt NPs/NG) with a low Pt loading of 3.5 wt . % and a Ni/Pt ratio of 0.038 : 1. Physical characterizations confirmed the presence of abundant atomic-scale vacancies in the Pt NPs induces long-range lattice distortions, and the Ni dopant generates a ligand effect resulting in electronic transfer from Ni to Pt. Experimental results and theoretical calculations indicated that atomic-scale vacancies mainly contributed the tolerance performances towards CO and CH3OH, the ligand effect derived from a tiny of Ni dopant accelerated the transformation from *O to *OH species, thereby improved the ORR activity without compromising the tolerance capabilities. Benefiting from the synergistic interplay between atomic-scale vacancies and ligand effect, as-prepared Vac-NiPt NPs/NG exhibited improved ORR activity, sufficient tolerance capabilities, and excellent durability. This study offers a new avenue for modulating the electrocatalytic activity of metal-based nanomaterials.

Harnessing the Synergistic Interplay between Atomic‐Scale Vacancies and Ligand Effect to Optimize the Oxygen Reduction Activity and Tolerance Performance

AbstractDefect engineering is an effective strategy for regulating the electrocatalysis of nanomaterials, yet it is seldom considered for modulating Pt‐based electrocatalysts for the oxygen reduction reaction (ORR). In this study, we designed Ni‐doped vacancy‐rich Pt nanoparticles anchored on nitrogen‐doped graphene (Vac‐NiPt NPs/NG) with a low Pt loading of 3.5 wt . % and a Ni/Pt ratio of 0.038 : 1. Physical characterizations confirmed the presence of abundant atomic‐scale vacancies in the Pt NPs induces long‐range lattice distortions, and the Ni dopant generates a ligand effect resulting in electronic transfer from Ni to Pt. Experimental results and theoretical calculations indicated that atomic‐scale vacancies mainly contributed the tolerance performances towards CO and CH3OH, the ligand effect derived from a tiny of Ni dopant accelerated the transformation from *O to *OH species, thereby improved the ORR activity without compromising the tolerance capabilities. Benefiting from the synergistic interplay between atomic‐scale vacancies and ligand effect, as‐prepared Vac‐NiPt NPs/NG exhibited improved ORR activity, sufficient tolerance capabilities, and excellent durability. This study offers a new avenue for modulating the electrocatalytic activity of metal‐based nanomaterials.

Ro5-4864, a translocator protein ligand, regulates T cell-mediated inflammatory responses in skin.

Translocator protein (TSPO) is a mitochondrial outer membrane protein expressed on a variety of immune cells, including macrophages, dendritic cells, and T cells, in addition to neurons and steroid-producing cells. Previous studies of TSPO ligands have suggested that TSPO is involved in multiple cellular functions, including steroidogenesis, immunomodulation, and cell proliferation. Currently, there are limited reports on the effects of TSPO or TSPO ligands on T cell-mediated immune responses. We here investigated the involvement of TSPO/TSPO ligand in T cell responses using a 2,4-dinitro-1-fluorobenzene (DNFB)-induced contact hypersensitivity (CH) model. Treatment with Ro5-4864, a TSPO ligand, during DNFB sensitization reduced the number and activation status of CD4+ and CD8+ T cells in draining lymph nodes and alleviated skin inflammation after DNFB challenge. Adoptive transfer of Ro5-4864-treated mouse-derived DNFB-sensitized T cells to naïve mice inhibited CH responses after DNFB challenge. Ro5-4864-treated sensitized T cells showed lower proliferative responses when stimulated with DNFB-pulsed antigen-presenting cells compared to control-treated sensitized T cells. Ro5-4864 also suppressed cell proliferation, as well as adenosine triphosphate and lactate production, during T cell activation. Moreover, the inhibitory effects of Ro5-4864 on T cell responses were conserved in TSPO-deficient cells. Our results suggest that Ro5-4864 inhibits CH responses by suppressing energy metabolism, at least via glycolysis, to reduce the T cell primary response in a TSPO-independent manner.

Engineering Chemical and Catalytic Activity of Metal Surface Sites by Controlling Strain and Ligand Effects in Nonmodel Nanoparticle Catalysts

Engineering Chemical and Catalytic Activity of Metal Surface Sites by Controlling Strain and Ligand Effects in Nonmodel Nanoparticle Catalysts

Cis-Dihydroxylation by Synthetic Iron(III)-Peroxo Intermediates and Rieske Dioxygenases: Experimental and Theoretical Approaches Reveal the Key O-O Bond Activation Step.

Dioxygen (O2) activation by iron-containing enzymes and biomimetic compounds generates iron-oxygen intermediates, such as iron-superoxo, -peroxo, -hydroperoxo, and -oxo, that mediate oxidative reactions in biological and abiological systems. Among the iron-oxygen intermediates, iron(III)-peroxo species are less frequently implicated as active intermediates in oxidation reactions. In this study, we present the combined experimental and theoretical investigations on cis-dihydroxylation reactions mediated by synthetic mononuclear nonheme iron-peroxo intermediates, demonstrating the importance of supporting ligands and metal centers in activating the peroxo ligand toward the O-O bond homolysis for the cis-dihydroxylation reactions. We found a significant ring size effect of the TMC ligand in [FeIII(O2)(n-TMC)]+ (TMC = tetramethylated tetraazacycloalkane; n = 12, 13, and 14) on the cis-dihydroxylation reactivity order: [FeIII(O2)(12-TMC)]+ > [FeIII(O2)(13-TMC)]+ > [FeIII(O2)(14-TMC)]+. Additionally, we found that only [FeIII(O2)(n-TMC)]+, but not other metal-peroxo complexes such as [MIII(O2)(n-TMC)]+ (M = Mn, Co, and Ni), is reactive for the cis-dihydroxylation of olefins. Using density functional theory (DFT) calculations, we revealed that electron transfer from the Fe dxz orbital to the peroxo σ*(O-O) orbital facilitates the O-O bond homolysis, with the O-O bond cleavage barrier well correlated with the energy gap between the frontier molecular orbitals of dxz and σ*(O-O). Further computational studies showed that the reactivity of the synthetic [FeIII(O2)(12-TMC)]+ complex is comparable to that of Rieske dioxygenases in cis-dihydroxylation, providing compelling evidence of the potential involvement of Fe(III)-peroxo species in Rieske dioxygenases. Thus, the present results significantly advance our understanding of the cis-dihydroxylation mechanisms by Rieske dioxygenases and synthetic nonheme iron-peroxo models.

Insights into the Synergistic Interplay of Ligand and Base Effects in Palladium-Catalyzed Enantioselectivity Hydrofunctionalization of Dienes.

Transition-metal-catalyzed enantioselective C-O bond constructions via hydrofunctionalization involving the use of O-based nucleophiles are an important topic in synthetic chemistry. Herein, density functional theory calculations were conducted to unveil the mechanism and enantioselectivity of Pd-catalyzed asymmetric hydrofunctionalization of conjugated dienes. We found that the base-assisted 4,3-activation model of the ligand-to-ligand hydrogen transfer (LLHT) mechanism is the most preferred one among all the cases, which could be ascribed to the favorable C-H···O interactions and the electrostatic interactions. For the enantioselective C-O bond formation process, the orientation of the substrate in the chiral pocket plays a significant role in controlling the enantioselectivity by contributing different noncovalent interactions. On the basis of the distortion/interaction model and energy decomposition analysis, the distortion energy is identified as the dominant factor controlling the product chemoselectivity. BnOH acts as the substrate, proton shuttle, and stabilizer to facilitate the H-transfer process in both LLHT and the C-O bond formation process. This study provides molecular-level insights into the collaborative effect of the base and P,N-ligand to perform the catalytic activity in the asymmetric hydrofunctionalization of conjugated dienes, which might open a new avenue for designing more efficient base-assisted enantioselective hydrofunctionalization by Pd catalysis.

DFT Study on Copper‐Catalyzed Hydroboration of 1,3‐Diynes: Mechanism, Selectivity, and Comparison with Ruthenium

Density functional theory calculations have been performed to explore the mechanism of copper‐catalyzed hydroboration of 1,3‐diyne with HBpin. The catalytic cycles are composed of three elementary processes in succession, namely, the generation of copper hydride species, migratory insertion and σ‐bond metathesis, among which the σ‐bond metathesis step is rate‐determining with a free‐energy barrier of 19.7 kcal/mol. The syn‐addition selectivity originates from the high barrier for converting (Z)‐product to (E)‐product. Effects of diphosphine ligands and substituents on the reactivity were also addressed. Lastly, this copper‐catalyzed hydroboration was compared with a related ruthenium‐catalyzed one, and the obtained results indicated that copper‐catalyzed hydroboration has a more favorable σ‐bond metathesis step but more challenging migratory insertion step as compared to the ruthenium‐catalyzed counterpart. Wavefunction analyses were performed to understand the observed behaviors.

DFT Investigation on Palladium-Catalyzed [2 + 2 + 1] Spiroannulation between Aryl Halides and Alkynes: Mechanism, Base Additive Role, and Solvent and Ligand Effects.

Transition metal-catalyzed spiroannulations are practical strategies for constructing spirocyclic skeletons of pharmaceutical and biological significance, yet the microscopic mechanism still lacks in-depth explorations. Here, the palladium-catalyzed [2 + 2 + 1] spiroannulation between aryl halides and alkynes was studied by employing the density functional theory (DFT) method. Based on comprehensive explorations on a couple of possible reaction pathways, it is found that the reaction probably experiences C-I oxidative addition, alkyne migration insertion, Cs2CO3-assisted aryl C-H activation, C-Br bond oxidative addition, C-C coupling, arene dearomatization and reductive elimination in sequence and leads to the formation of the spiro[4,5]decane pentacyclic product (P) ultimately. Among these, the C-Br bond oxidative addition step acts as the rate-determining step (RDS) of the whole reaction, featuring a practical free energy barrier of 32.4 kcal·mol-1 at 130 °C. Computationally predicted kinetics such as half-life transferred from the RDS step's barrier on the optimal reaction pathway (1.2 × 101 h) coincides well with corresponding experimental results (91% yield of the spiro[4,5]decane pentacyclic product P after reacting 10 h at 130 °C). In addition, theoretical predictions regarding the solvent/ligand effects and base additive role in the reaction, rationalized by distortion-interaction/natural population/noncovalent interaction analyses, are also in good agreement with experimental data and trend. This good agreement between experiment and theory makes sense for new designations and further experimental improvements of such Pd-catalyzed transformations.