A predictive approach for driving down machine learning model errors is introduced and demonstrated across discovery inorganic organic chemistry.

The development of new catalysts for selective nitrene transfer is a continuing area interest. In particular, the ability to control chemoselectivity intermolecular reactions in presence multiple reactive sites has been long-standing challenge field. this paper, we demonstrate examples silver-catalyzed, nondirected, that are both chemoselective and flexible aziridination or C–H insertion, depending on choice ligand. Experimental probes present puzzling picture mechanistic details pathways...

Recent transformative advances in computing power and algorithms have made computational chemistry central to the discovery design of new molecules materials. First-principles simulations are increasingly accurate applicable large systems with speed needed for high-throughput screening. Despite these strides, combinatorial challenges associated vastness chemical space mean that more than just fast tools accelerated discovery. In transition-metal catalysis, unique arise. The variable spin,...

Dirhodium-catalyzed C-H amination is hypothesized to proceed via Rh2-nitrene intermediates in either the Rh2(II,II) or Rh2(II,III) redox state. Herein, we report joint theoretical and experimental studies of ground electronic state (GES), potentials, [Rh2(II,III)(O2CCH3)4(L)n](+) (1_L) (L = none, Cl(-), H2O), [Rh2(esp)2](+) (2), Rh2(espn)2Cl (3) (esp α,α,α',α'-tetramethyl-1,3-benzenedipropanoate espn α,α,α',α'-tetramethyl-1,3-benzenedipropanamidate). CASSCF calculations on 1_L yield a wave...

Discerning the factors that control reactivity of high-valent metal-oxo species is critical to both an understanding metalloenzyme and related transition metal catalysts. Computational studies have suggested excited higher spin state in a number can provide lower energy barrier for oxidation reactions, leading conclusion this unobserved complex should be considered as active oxidant. However, testing these computational predictions by experiment difficult has rarely been accomplished....

Addition of anionic donors to the manganese(V)-oxo corrolazine complex Mn(V)(O)(TBP8Cz) has a dramatic influence on oxygen-atom transfer (OAT) reactivity with thioether substrates. The six-coordinate [Mn(V)(O)(TBP8Cz)(X)](-) complexes (X = F(-), N3(-), OCN(-)) exhibit ∼5 cm(-1) downshift Mn-O vibrational mode relative parent as seen by resonance Raman spectroscopy. Product analysis shows that oxidation substrates gives sulfoxide product, consistent single OAT. A wide range OAT is for...

Determination of ground-state spins open-shell transition-metal complexes is critical to understanding catalytic and materials properties but also challenging with approximate electronic structure methods. As an alternative approach, we demonstrate how alone can be used guide assignment spin from experimentally determined crystal structures complexes. We first identify the limits distance-based heuristics distributions metal-ligand bond lengths over 2000 unique mononuclear Fe(II)/Fe(III) To...

Nitrene transfer (NT) reactions represent powerful and direct methods to convert C-H bonds into amine groups that are prevalent in many commodity chemicals pharmaceuticals. The importance of the C-N bond has stimulated development numerous transition-metal complexes effect chemo-, regio-, diastereoselective NT. An ongoing challenge is understand how subtle interactions between catalyst substrate influence site-selectivity amination event. In this work, we explore underlying reasons why...

The new ligand N3PyamideSR and its FeII complex [FeII(N3PyamideSR)](BF4)2 (1) are described. Reaction of 1 with PhIO at −40 °C gives metastable [FeIV(O)(N3PyamideSR)]2+ (2), containing a sulfide single amide H-bond donor in proximity to the terminal oxo group. Direct evidence for H-bonding is seen structural analogue, [FeII(Cl)(N3PyamideSR)](BF4)2 (3). Complex 2 exhibits rapid O-atom transfer (OAT) toward external substrates, but no intramolecular OAT. However, direct S-oxygenation does...

Solvate ionic liquids (SIL) have promising applications as electrolyte materials and machine learning can help accelerate the virtual screening of candidate molecules for SIL.

Single atom catalysts (SACs) are emergent catalytic materials that have the promise of merging scalability heterogeneous with high activity and economy homogeneous catalysts. Computational, first-principles modeling can provide essential insight into SAC mechanism active site configuration, where sub-nm-scale environment challenge even highest-resolution experimental spectroscopic techniques. Nevertheless, very properties make SACs attractive in catalysis, such as localized d electrons...

This study focuses on enhancing the water oxidation reaction (WOR) efficacy of dinuclear cobalt complex catalysts from both kinetic (turnover frequency, TOF) and thermodynamic (overpotential, η) perspectives. For this purpose, we synthesized six complexes 1-6 comprising non-innocent ligands with different electronically active substituents (-OMe (1), -Me (2), -H (3), -F (4), -Cl (5), -CN (6)). The electronic effects electrochemical WOR under neutral, acidic, alkaline conditions were...

The addition of Lewis or Brönsted acids (LA = Zn(OTf)2, B(C6F5)3, HBArF, TFA) to the high-valent manganese-oxo complex MnV(O)(TBP8Cz) results in stabilization a valence tautomer MnIV(O-LA)(TBP8Cz•+). ZnII and B(C6F5)3 complexes were characterized by manganese K-edge X-ray absorption spectroscopy (XAS). position edge energies intensities pre-edge (1s 3d) peaks confirm that Mn ion is +4 oxidation state. Fitting extended fine structure (EXAFS) region reveals 4 N/O ligands at Mn-Nave 1.89 Å...

This paper describes the influence of replacement one rhodium atoms by bismuth in a chiral dirhodium tetracarboxylate catalyst on asymmetric induction cyclopropanation and C–H functionalization chemistry trichloroethyl aryldiazoacetates. The ligand used this study is S-tert-butylsulphonylprolinate (S-TBSP), which was first highly enantioselective catalyst. Even though Rh atom with Bi has changed electronic properties system, RhBi complexes have several similarities to corresponding Rh2...

<p>Machine learning (ML) models, such as artificial neural networks, have emerged a complement to high-throughput screening, enabling characterization of new compounds in seconds instead hours. The promise ML models enable large-scale, chemical space exploration can only be realized if it is straightforward identify when molecules and materials are outside the model’s domain applicability. Established uncertainty metrics for network either costly obtain (e.g., ensemble models) or rely...

The non-heme iron complexes, [FeII(N3PySR)(CH3CN)](BF4)2 (1) and [FeII(N3PyamideSR)](BF4)2 (2), afford rare examples of metastable Fe(III)-OOH Fe(III)-OOtBu complexes containing equatorial thioether ligands a single H-bond donor in the second coordination sphere. These peroxo were characterized by range spectroscopic methods density functional theory studies. influence ligand one on stability properties these was investigated.

Three new diruthenium oxyanion complexes have been prepared, crystallographically characterized, and screened for their potential to photochemically unmask a reactive Ru-Ru═O intermediate. The most promising candidate, Ru2(chp)4ONO2 (4, chp = 6-chloro-2-hydroxypyridinate), displays set of signals centered around m/z 733 amu in its MALDI-TOF mass spectrum, consistent with the formation [Ru2(chp)4O](+) ([6](+)) ion. These shift 735 4*, which contains an (18)O-labeled nitrate. EPR spectroscopy...

<p>Determination of ground-state spins open-shell transition metal complexes is critical to understanding catalytic and materials properties but also challenging with approximate electronic structure methods. As an alternative approach, we demonstrate how alone can be used guide assignment spin from experimentally determined crystal structures complexes. We first identify the limits distance-based heuristics distributions metal–ligand bond lengths over 2,000 unique mononuclear...

Construction of nitrogen–nitrogen triple bonds via homocoupling metal nitrides is an important fundamental reaction relevant to a potential Nitrogen Economy. Here, we report that room temperature photolysis Ru2(chp)4N3 (chp– = 2-chloro-6-hydroxypyridinate) in CH2Cl2 produces N2 reductive coupling Ru2(chp)4N nitrido species. Computational analysis reveals the nitride transition state (TS) features out-of-plane "zigzag" geometry instead anticipated planar zigzag TS. However, with intentional...

Abstract Addition of an anionic donor to Mn V (O) porphyrinoid complex causes a dramatic increase in 2‐electron oxygen‐atom‐transfer (OAT) chemistry. The 6‐coordinate [Mn (O)(TBP 8 Cz)(CN)] − was generated from addition Bu 4 N + CN the 5‐coordinate precursor. cyanide‐ligated characterized for first time by K‐edge X‐ray absorption spectroscopy (XAS) and gives MnO=1.53 Å, MnCN=2.21 Å. In combination with computational studies these distances were shown correlate singlet ground state....

The scission of the O-O bond in O2 during respiration and formation photosynthesis are engines aerobic life. Likewise, reduction oxidation reduced oxygen species to form indispensable components for emerging renewable technologies, including energy storage conversion, yet discrete molecule-like systems that promote these fundamental reactions rare. Herein, we report a square-planar tetramanganese cluster formed by self-assembly within metal-organic framework reversibly reduces four...

This study showcases the integration of experimental and theoretical approaches for optimizing biosensor.

Automated patent mining creates domain-specific datasets of molecular structures for generative modeling with limited human intervention.

Abstract In this study, dinuclear cobalt complexes ( 1 and 2 ) featuring bis(benzimidazole)pyrazolide‐type ligands H L Me were prepared evaluated as molecular electrocatalysts for water oxidation. Notably, bearing a non‐innocent ligand displayed faster catalytic turnover than under alkaline conditions, the base dependence of oxidation kinetic isotope effect analysis indicated that reaction mediated by proceeded different mechanism relative to . Spectroelectrochemical, cold‐spray ionization...

Electrochemical water oxidation is known as the anodic reaction of splitting. Efficient design and earth-abundant electrocatalysts are crucial to this process. Herein, we report a family catalysts (1–3) bearing bis(benzimidazole)pyrazolide ligands (H2L1–H2L3). H2L3 contains electron-donating substituents noninnocent components, resulting in catalyst 3 exhibiting unique performance. Kinetic studies show first-order kinetic dependence on [3] [H2O] under neutral alkaline conditions. In contrast...