c-h bond activation

Microorganisms have long captivated researchers for their potential to produce enzymes with diverse industrial applications. Efficient production of proteases from new strains is crucial as these enzymes play a vital role in breaking down protein bonds, enabling their use in industrial applications. Therefore, a novel Exiguobacterium indicum 1.2.3 was isolated (Istanbul, Turkiye) and characterized in this study. This strain produced alkaline serine protease, which works in lower temperatures (20-40 °C) with casein as a specific substrate...

This study focuses on addressing the challenges in the dry reforming of propane, a process historically marked by low syngas yields and only moderate conversions of CO2 and propane. The primary objective was to enhance CO2 utilization and boost the selectivity of syngas (CO and H2 ) production using titania-based catalysts. For synthesizing these catalysts, an impregnation method was employed with subsequent characterization through X-ray diffraction (XRD), N2 adsorption-desorption, ammonia temperature-programmed desorption (TPD), and hydrogen temperature-programmed reduction (TPR)...

The electrochemical nitrate reduction reaction (NO3 - RR) is a novel green method for ammonia synthesis. However, the lack of sufficient catalysts has hindered the development of the NO3 - RR. This research develops a transformation of porous CoP@N-C/CC into porous phosphorus-rich CoP4 @N-C/CC through high-temperature calcination. Due to its unique phosphating-rich structure, CoP4 @N-C/CC exhibits an excellent Faraday efficiency (FE: 92.3%) and NH3 yield (610.2 μmol h-1 cm-2 ). Such a catalyst with more P-P bonds can provide more active sites, effectively enhancing the adsorption and reaction processes of reactant molecules...

This study focuses on the development of regiospecific hydroarylation polyaddition of naphthalene- and carbazole-based monomers with diynes under mild reaction conditions at room temperature. A 1-pyrazole substituent serves as an appropriate directing group for a Co-catalyst to efficiently activate the C-H bonds of generally inactive six-membered aromatic hydrocarbons. The 1-pyrazole groups in 2,6-di(1-pyrazolyl)naphthalene adopt planar conformations and act as directing groups, resulting in a smooth hydroarylation reaction...

High-valent Fe(IV)=O intermediates of metalloenzymes have inspired numerous efforts to generate synthetic analogs to mimic and understand their substrate oxidation reactivities. However, high-valent M(IV) complexes of late transition metals are rare. We have recently reported a novel Co(IV)-dinitrate complex (1-NO3) that activates sp3 C-H bonds up to 87 kcal/mol. In this work, we have shown that the nitrate ligands in 1-NO3 can be replaced by azide, a more basic coordinating base, resulting in the formation of a more potent Co(IV)-diazide species (1-N3) that reacts with substrates (hydrocarbons and phenols) at faster rate constants and activates stronger C-H bonds than the parent complex 1-NO3...

The global concern surrounding pollution caused by phthalates is escalating, with dimethyl phthalate (DMP) emerging as one of the most prevalent contaminants within the phthalates (PAEs) category. Although the biodegradation of DMP is considered both safe and efficient, its underlying degradation mechanism is not yet fully elucidated, and the degradation performance can be somewhat inconsistent. To address this issue, our study isolated a DMP-degrading bacterium (DNM-S1) from a vegetable greenhouse. The resulting data revealed that DNM-S1 exhibited a remarkable degradation performance, successfully degrading 84...

A tetradentate bis(amido)bis(phosphine) FeII complex, (PNNP)Fe, is shown to activate the terminal C-H bond of aryl alkynes across its Fe-Namide bonds. (PNNP)Fe is also shown to catalytically dimerize terminal aryl alkynes to produce 1,3-enynes with Z  :  E ratios as high as 96 : 4 with yields up to 95% and loadings as low as 1 mol% at 30 °C in 2 h. A plausible metal-ligand cooperative mechanism invoking a vinylidene intermediate is proposed.

The lack of intrinsic active sites for photocatalytic CO2 reduction reaction (CO2 RR) and fast recombination rate of charge carriers are the main obstacles to achieving high photocatalytic activity. In this work, a novel phosphorus and boron binary-doped graphitic carbon nitride, highly porous material that exhibits powerful photocatalytic CO2 reduction activity, specifically toward selective CO generation, is disclosed. The coexistence of Lewis-acidic and Lewis-basic sites plays a key role in tuning the electronic structure, promoting charge distribution, extending light-harvesting ability, and promoting dissociation of excitons into active carriers...

The C-H bond activation catalyzed by a manganese(I) complex has achieved significant development but is limited to C(sp2 )-H bonds. In this work, an efficient manganese(I)-catalyzed direct nucleophilic addition reaction of C(sp3 )-H bonds to aromatic aldehydes has been developed. This is the first example of manganese(I)-catalyzed C(sp3 )-H bond transformation. A manganacycle complex was isolated and proved to be the key active intermediate in the catalytic cycle.

Tetrapyridyl-functionalized phosphinines were prepared and structurally characterized. The donor-functionalized aromatic phosphorus heterocycles react highly selectively and even reversibly with water. Calculations reveal P,N-cooperativity for this process, with the flanking pyridyl groups serving to kinetically enhance the formal oxidative addition process of H2 O to the low-coordinate phosphorus atom via H-bonding. Subsequent tautomerization forms 1,2-dihydrophosphinine derivatives, which can be quantitatively converted back to the phosphinine by applying vacuum, even at room temperature...

Antiretroviral drugs (ARVDs) have been extensively employed in health care to improve the quality of life and lifecycle longevity. However, overuse and improper disposal of ARVDs have been recognized as an emerging concern whereby wastewater treatment major recipients. Therefore, in this work, the activated macadamia nutshells (MCNs) were explored as low-cost adsorbents for the removal of ARVDs in wastewater samples. Fourier transform infrared spectroscopy (FTIR), Scanning Electron microscopy (SEM), Brunauer-Emmet-Teller (BET), and Powder X-ray diffraction (PXRD)...

Lysine dioxygenase (KDO) is an important enzyme in human physiology involved in bioprocesses that trigger collagen cross-linking and blood pressure control. There are several KDOs in nature; however, little is known about the factors that govern the regio- and stereoselectivity of these enzymes. To understand how KDOs can selectively hydroxylate their substrate, we did a comprehensive computational study into the mechanisms and features of 4-lysine dioxygenase. In particular, we selected a snapshot from the MD simulation on KDO5 and created large QM cluster models ( A , B , and C ) containing 297, 312, and 407 atoms, respectively...

An unprecedented solvent-tuned electrochemical method for selective C(sp3 )-H bond activation towards the synthesis of C3 functionalized chromone derivatives has been developed. This electrosynthesis protocol provides an efficient and green way to access various C3-functionalized chromones by avoiding traditionally employed transition metals and high temperatures. The swappable chemoselectivity was controlled mainly by altering the solvent and the current. A plausible reaction mechanism has been proposed with the help of radical capture and cyclic voltammetry experiments...

We present herein the synthesis, characterization and complexation of ferrocenyl-substituted MIIs (mesoionic imines) and their metal complexes. In the free MIIs, strong hydrogen bonding interactions are observed between the imine-N and the C-H bonds of the ferrocenyl substituents both in the solid state and in solution. The influence of this hydrogen bonding is so strong that complexation of the MIIs with [IrCp*Cl2]2 yields unique six-membered iridacycles via C-H-activation of the corresponding C-H-site at the Fc-substituent and not the Ph-substituent...

Exploitation of noncovalent interactions for recognition of an organic substrate has received much attention for the design of metal catalysts in organic synthesis. The CH-π interaction is especially of interest for molecular recognition because both the C-H bonds and the π electrons are fundamental properties of organic molecules. However, because of their weak nature, these interactions have been less utilized for the control of organic reactions. We show here that the CH-π interaction can be used to kinetically accelerate catalytic C-H activation of arenes by directly recognizing the π-electrons of the arene substrates with a spirobipyridine ligand...

The direct oxidation of CH4 to C2 H5 OH is attractive but challenging owing to the intricate processes involving carbon-chain growth and hydroxylation simultaneously. The inherent difficulty arises from the strong tendency of CH4 to overoxidize in the commonly used pressurized powder suspension systems rich in reactive oxygen radicals (ROR), which are specifically designed for CH4 concentration and activation. Meanwhile, the strong tendency of nucleophilic attack of potent ROR on the C-C bond of the resulting product C2 H5 OH ultimately leads to a higher selectivity for C1 oxygenates...

Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods for their functionalization require them to first be converted into a more activated derivative, while recent years have seen a vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can be used toward this goal. These transformations are broadly classified into three categories. Deoxygenative functionalizations, representing derivatization of the C-O bond, enable the alcohol to act as a leaving group toward the formation of new C-C bonds...

The construction of C(sp3)-N bonds via direct N-centered radical addition with olefins under benign conditions is a desirable but challenging strategy. Herein, we describe an organo-photocatalytic approach to achieve anti-Markovnikov alkene hydroamidation with sulfonyl azides in a highly efficient manner under transition-metal-free and mild conditions. A broad range of substrates, including both activated and unactivated alkenes, are suitable for this protocol, providing a convenient and practical method to construct sulfonylamide derivatives...

The Cu-O-Cu core exhibits methane-to-methanol conversion, mirroring the reactivity of the copper-containing enzyme pMMO. Herein, we computationally examined the reactivity of a biomimetic Cu-O-Cu core towards methane-to-methanol conversion. The oxygen atom of the Cu-O-Cu core abstracts hydrogen present in the C-H bond of methane. The spin density at the bridging oxygen helps to abstract hydrogen from the C-H bond. We modulated the spin density of the bridging oxygen by substituting only a single copper atom of the Cu-O-Cu core by metals (M) such as Fe, Co, and Ag...

Non-oxidative methane dehydro-aromatization reaction can co-produce hydrogen and benzene effectively on a molybdenum-zeolite based thermochemical catalyst, which is a very promising approach for natural-gas upgrading. However, the low methane conversion and aromatics selectivity and weak durability restrain the realistic application for industry. Here, a mechanism for enhancing catalysis activity on methane activation and carbon-carbon bond coupling has been found to promote conversion and selectivity simultaneously by adding platinum-bismuth alloy cluster to form a trimetallic catalyst on zeolite (Pt-Bi/Mo/ZSM-5)...