Unraveling the Prominent Existence of Trace Metals in Photocatalysis: Exploring Iron Impurity Effects.

Metal impurities can complicate the identification of active catalyst species in transition metal catalysis and electrocatalysis, potentially leading to misleading findings. This study investigates the influence of metal impurities on photocatalysis. Specifically, the photocatalytic reaction of inert alkanes using chlorides without the use of an external photocatalyst was studied, achieving successful C(sp3)-H functionalization. The observations reveal that Fe and Cu impurities are challenging to avoid in a typical laboratory environment and are prominently present in normal reaction systems, and iron impurities play a dominant role in the aforementioned apparent 'metal-free' reaction. Additionally, iron exhibits significantly higher catalytic activity compared to Cu, Ce, and Ni at low metal concentrations in the photocatalytic C(sp3)-H functionalization using chlorides. Considering the widespread presence of Fe and Cu impurities in typical laboratory environments, this study serves as a reminder of their involvement in reaction processes.

Cobalt catalyzed practical hydroboration of terminal alkynes with time-dependent stereoselectivity.

Stereodefined vinylboron compounds are important organic synthons. The synthesis of E-1-vinylboron compounds typically involves the addition of a B-H bond to terminal alkynes. The selective generation of the thermodynamically unfavorable Z-isomers remains challenging, necessitating improved methods. Here, such a proficient and cost-effective catalytic system is introduced, comprising a cobalt salt and a readily accessible air-stable CNC pincer ligand. This system enables the transformation of terminal alkynes, even in the presence of bulky substituents, with excellent Z-selectivity. High turnover numbers (>1,600) and turnover frequencies (>132,000 h-1) are achieved at room temperature, and the reaction can be scaled up to 30 mmol smoothly. Kinetic studies reveal a formal second-order dependence on cobalt concentration. Mechanistic investigations indicate that the alkynes exhibit a higher affinity for the catalyst than the alkene products, resulting in exceptional Z-selective performance. Furthermore, a rare time-dependent stereoselectivity is observed, allowing for quantitative conversion of Z-vinylboronate esters to the E-isomers.

Terminal C(sp3)-H borylation through intermolecular radical sampling.

Hydrogen atom transfer (HAT) processes can overcome the strong bond dissociation energies (BDEs) of inert C(sp3)-H bonds and thereby convert feedstock alkanes into value-added fine chemicals. Nevertheless, the high reactivity of HAT reagents, coupled with the small differences among various C(sp3)-H bond strengths, renders site-selective transformations of straight-chain alkanes a great challenge. Here, we present a photocatalytic intermolecular radical sampling process for the iron-catalyzed borylation of terminal C(sp3)-H bonds in substrates with small steric hindrance, including unbranched alkanes. Mechanistic investigations have revealed that the reaction proceeds through a reversible HAT process, followed by a selective borylation of carbon radicals. A boron-sulfoxide complex may contribute to the high terminal regioselectivity observed.

Micro FT-IR spectroscopic measurements of CH4: Experimental calibration with high-pressure and high temperature optical cell (HPOC).

Fourier transform infrared spectroscopy (FTIR) is a prevalent nondestructive in situ analytical technique widely employed for the qualitative characterization of natural fluid inclusions. Presently, the quantitative determination of the temperature, pressure, and composition of natural inclusions stands as a pivotal challenge in the geological application of laser spectroscopy. Through the integration of the capillary high-pressure optical cell (HPOC) technique and Fourier transform infrared spectroscopy, infrared quantitative models for the C-H symmetric stretching band (v3) in the vapor phase of CH4 under varying temperature (40-200 °C) and pressure (20-500 bar) conditions are established for the first time. This accomplishment is achieved through fitting and calculation of infrared spectra. A linear quantitative relationship and the dynamic evolution of infrared spectral parameters (peak area, full width at half maximum, peak height ratio, and peak shifts) concerning temperature, pressure, and density are meticulously investigated. The findings reveal that the peak area and full width at half maximum exhibit an upward trend with increasing pressure and density, and are inversely proportional to temperature. The height ratio (P band/Q band, R band/Q band) experiences an increase as density escalates. Moreover, the CH4v3 band position shows a higher wavenumber shift with increasing temperature, while its position correlates negatively with pressure and density. Thus, this method demonstrates its applicability in deducing the PVT-x properties of CH4-bearing systems, including CH4-rich fluid inclusions, CH4 content within hydrocarbon inclusions, and experimental fluid investigations. In contrast to the Raman quantitative approach, the infrared quantitative formula can be universally adopted in any infrared laboratory owing to the quantitative theory (Beer-Lambert law) governing infrared absorption spectra. By collecting Raman spectra and infrared spectra of pure methane fluid inclusions from the central region of the Alps and subsequently calculating the results using two distinct quantitative methods for fluid inclusions, we have demonstrated the feasibility of applying infrared spectroscopy in natural fluid inclusion studies.

Iron-catalyzed deconstructive alkylation through chlorine radical induced C-C single bond cleavage under visible light.

Selective C-C single bond cleavage of simple compounds is a highly challenging and desired process. Herein, a chlorine radical-induced deconstructive C-C bond alkylation with alcohols and alkenes catalyzed by iron salts was reported for the first time. Readily available alcohols and various electron-deficient alkenes were tolerated. Late-stage and large-scale reactions proceed smoothly. This catalyst system shows potential for diversified deconstructive functionalization of simple C-C bonds.

Visible Light-Induced Unactivated δ-C(sp3 )-H Amination of Alcohols Catalyzed by Iron.

An iron-catalyzed remote C(sp3 )-H amination of alcohols through 1,5-hydrogen atom transfer is developed. This protocol provides a method to generate δ-C(sp3 )-N bonds from primary, secondary, and tertiary alcohols under mild conditions. A wide substrate scope and a good functional group tolerance are presented. Mechanistic studies show that a LMCT course of an Fe-OR species and a chlorine radical-induced hydrogen abstraction of an alcohol are possible to generate the alkoxy radical intermediate.

Visible-Light-Induced Decarboxylative Fluorination of Aliphatic Carboxylic Acids Catalyzed by Iron.

An efficient and inexpensive protocol for the direct decarboxylative fluorination of aliphatic carboxylic acids catalyzed with iron salts under visible light is presented. This new method allows the facile fluorination of a diverse array of carboxylic acids even on gram scale using a Schlenk flask without loss of efficiency. Mechanistic studies suggest that the photoinduced ligand-to-metal charge transfer process enables the generation of the key step to generate the carboxyl radical intermediates.

Carbazoles in Oils, and Their Application in Identifying Oil Filling Pathways in Eocene Syn-Rift Fault Blocks in the Dongpu Depression, Bohai Bay Basin, East China.

Carbazoles and dimethyl carbazoles (DMCs) are important nitrogen heterocyclic aromatic compounds in oils and sedimentary rock extracts. Based on both migration fractionation effects and differences in the thermal stability of their isomers, carbazoles can be used to trace oil migration orientations and filling pathways. Molecular biomarker compositions indicate that all oils and oil-bearing sand extracts in the Eocene fault-blocked reservoirs of the Huzhuangji area (Western Slope Belt) of the Dongpu Depression (Bohai Bay Basin, East China) belong to a single oil population. In this study, four geochemical indicators relating to carbazoles, namely (a) 1,8-/2,7-dimethyl carbazoles (1,8-/2,7-DMC); (b) 1,8-/2,5-dimethyl carbazoles (1,8-/2,5-DMC); (c) 1,8-/N-exposed dimethyl carbazoles (1,8-/N-exposed DMC); and (d) G1 N-shielded %, were applied to trace oil migration orientations and filling pathways. The results show that these parameter values gradually increase toward the Hu-5 fault block at the structural high. The measured values from the subsurface are consistent with the results calculated from the molecular adsorption modeling. Therefore, it is concluded that the relative parameters of dimethyl carbazoles are practical molecular indicators for tracing oil migration orientations and filling pathways in syn-rift fault-blocked reservoirs.

Iron-Catalyzed C-C Single-Bond Cleavage of Alcohols.

An iron-catalyzed deconstruction/hydrogenation reaction of alcohols through C-C bond cleavage is developed through photocatalysis, to produce ketones or aldehydes as the products. Tertiary, secondary, and primary alcohols bearing a wide range of substituents are suitable substrates. Complex natural alcohols can also perform the transformation selectively. A investigation of the mechanism reveals a procedure that involves chlorine radical improved O-H homolysis, with the assistance of 2,4,6-collidine.

Selective Degradation of Styrene-Related Plastics Catalyzed by Iron under Visible Light*.

Efficient degradation of plastics, the vital challenge for a sustainable future, stands in need of better chemical recycling procedures that help produce commercially valuable small molecules and redefine plastic waste as a rich source of chemical feedstock. However, the corresponding chemical recycling methods, while being generally restricted to polar polymers, need improvement. Particularly, degradation of chemically inert nonpolar polymers, the major constitutes of plastics, suffers from low selectivity and very harsh transformation conditions. Herein, an efficient method was developed for selective degradation of styrene-related plastics under gentle conditions through multiple oxidation of sp3 C-H bonds and sp3 C-C bonds. The procedure was catalyzed with inexpensive iron salts under visible light, using oxygen as green oxidant. Furthermore, simple iron salts could be used to degrade plastics in the absence of solvent under natural conditions, highlighting the potential application of iron salts as additives for degradable plastics.

Methyltrimethyltridecylchromans in Mature Oils from Saline Lacustrine Settings in the Dongpu Depression, Bohai Bay Basin, East China.

The measured composition and distribution of methyltrimethyltridecylchroman (MTTC) compounds in the crude oils from Wenliu (salt-rich zone) and Machang (salt-free zone) areas of the Dongpu Depression were correlated with redox conditions and paleosalinity. The oil samples derived from the mesosaline environment were found with all alkylated MTTC series present. In addition, the dimethyl MTTCs developed more favorably in the oils derived from a relatively reducing and hypersaline environment (Wenliu) compared to those from the fresh lacustrine settings (Machang), while the trimethyl MTTCs developed more favorably in the fresh water environment (Machang). Determination of the oil maturity in the "oil window" by a series of aromatic maturity indicators suggests that MTTC compounds are not only present in immature or low-mature oils but also distributed in mature oils. Therefore, the "low-mature" oil found with abundant MTTC compounds, especially derived from the saline lacustrine settings, should be assessed with caution.

Cage-confined photocatalysis for wide-scope unusually selective [2 + 2] cycloaddition through visible-light triplet sensitization.

Light-induced [2 + 2] cycloaddition is the most straightforward way to generate cyclobutanes, which are core structures of many natural products, drugs and bioactive compounds. Despite continuous advances in selective [2 + 2] cycloaddition research, general method for intermolecular photocatalysis of acyclic olefins with specific regio- and diastereoselectivity, for example, syn-head-to-head (syn-HH) cyclobutane derivatives, is still lack of development but highly desired. Herein, we report a cage-confined photocatalytic protocol to enable unusual intermolecular [2 + 2] cycloaddition for α,ß-unsaturated carbonyl compounds. The syn-HH diastereomers are readily generated with diastereoselectivity up to 99%. The cage-catalyst is highly efficient and robust, covering a diverse substrate range with excellent substituent tolerance. The mimic-enzyme catalysis is proposed through a host-guest mediated procedure expedited by aqueous phase transition of reactant and product, where the supramolecular cage effect plays an important role to facilitate substrates inclusion and pre-orientation, offering a promising avenue for general and eco-friendly cycloaddition photocatalysis with special diastereoselectivity.

Thiophene Cation Intercalation to Improve Band-Edge Integrity in Reduced-Dimensional Perovskites.

The insertion of large organic cations in metal halide perovskites with reduced-dimensional (RD) crystal structures increases crystal formation energy and regulates the growth orientation of the inorganic domains. However, the power conversion performance is curtailed by the insulating nature of the bulky cations. Now a series of RD perovskites with 2-thiophenmethylammonium (TMA) as the intercalating cation are investigated. Compared with traditional ligands, TMA demonstrates improved electron transfer in the inorganic framework. TMA modifies the near-band-edge integrity of the RD perovskite, improving hole transport. A power conversion efficiency of 19 % is achieved, the highest to date for TMA-based RD perovskite photovoltaics; these TMA devices provide a 12 % relative increase in PCE compared to control RD perovskite devices that use PEA as the intercalating ligand, a result of the improved charge transfer from the inorganic layer to the organic ligands.