RESUMO
Metalla-aromatics are important complexes that show unique properties owing to their highly conjugated systems, which show Hückel or Möbius aromaticity. Recently, several metalla-aromatics showing spiro-aromaticity or σ-aromaticity have been reported. Herein, we report the isolation of the first cyclopropametallanaphthalenes, in which the metallacyclopropene ring shows σ-aromaticity and weak hyperconjugative aromaticity. The reaction of OsCl2 (PPh3 )3 with o-ethynylphenyl alkynes in the presence of PPh3 followed by protonation with HCl yielded the first cyclopropametallanaphthalenes. The reaction mechanism and the aromaticity were also investigated by density functional theory studies.
RESUMO
This paper mainly focuses on the synergistic effect of Sn and N dopants to enhance the photocatalytic performance of anatase TiO2 under visible light or simulated solar light irradiation. The Sn and N co-doped TiO2 (SNT-x) photocatalysts were successfully prepared by the facile sol-gel method and the post-nitridation route in the temperature range of 400-550 °C. All the as-prepared samples were characterized in detail by X-ray diffraction, UV-vis diffuse reflectance spectroscopy, transmission electron microscopy, X-ray photoelectron and electron spin resonance spectroscopy and photoelectrochemical measurements. The characterization results reveal that the co-incorporation of Sn and N atoms remarkably modifies the electronic structure of TiO2, which gives rise to a prominent separation of photogenerated charge carriers and more efficient interfacial charge-transfer reactions in a photocatalytic process. The enhanced photocatalytic activity is attributed to the intensified active oxygen species including hydroxyl radicals (ËOH) and superoxide anion radicals (O2Ë(-)) for degradation of organic pollutants. And the result of photocatalytic hydrogen production further confirms the existence of the synergistic effect in the SNT-x samples, because they exhibit higher photocatalytic activity than the sum of N/TiO2 and Sn/TiO2. This work provides a paradigm to consolidate the understanding of the synergistic effect of metal and non-metal co-doped TiO2 in domains of photocatalysis and photoelectrochemistry.
RESUMO
The safety citizenship behavior (SCB) of construction workers can improve project safety performance. This study explored how construction company owners' safety management behavior contributes to the development and encouragement of SCB. It combined the Job Demands-Resources (JD-R) and Stimulus-Organism-Response (SOR) theories to propose relevant hypotheses and develop a theoretical model to examine the effect of owners' safety management behavior on construction workers' SCB. Data from 534 construction workers were collected through questionnaires. Confirmatory Factor Analysis (CFA) and the Structural Equation Model (SEM) were used for empirical analysis. It was found that the owner's safety management behavior positively affected the construction workers' SCB. In particular, work engagement played an intermediary role, while power distance exhibited a moderating effect. A few noteworthy findings are that proactive safety behavior is significantly positively influenced by organization and coordination, prosocial safety behavior is significantly positively influenced by safety funding investment, and high power distance is not always bad for construction workers' safety citizenship behavior. By determining the connection between owners' safety management behavior and construction workers' SCB, this study offered a fresh perspective on promoting construction workers' proactive behavior and put forward suggestions for owners to improve project safety management.
RESUMO
Four diaza-osmapentalenes were prepared by two-step reactions, through the treatment of an alkyne-coordinated osmium complex with azo compounds, followed by the addition of AgSbF6/CO. Their aromaticity was confirmed by crystal parameters, NMR spectra and theoretical calculations. These complexes are the first diaza-metallapentalenes representing a new class of metallaaromatics.
RESUMO
Aromatic metallacycles are of considerable current interest. Reported aromatic metallacycles are mainly those with carbon, nitrogen, oxygen and sulfur. In this work, we report the synthesis and characterization of aromatic chloroosmacyclopentatrienes, which represent the first structurally confirmed metallaaromatic with a chlorine atom in its framework. Single-crystal X-ray diffraction studies show that these planar chloroosmacyclopentatrienes possess a very short Os-ClC distance suggesting M=ClC bond character.
RESUMO
Treatment of the SiMe3 -protected dichloro-rhenium carbyne complexes Re{≡CCH=C(R)C≡CSiMe3 }Cl2 (PMe2 Ph)3 (R = CMe3 , 1-adamantyl) with CsF in methanol directly afforded the 12-membered metallacycles {ReCl(PMe2 Ph)3 }2 {≡CCH=C(R)C≡C-}2 . The electronic structure of the metallacycle was investigated by density functional calculations. The UV-vis spectrum of the metallacycle shows a red-shifted band compared to that of the starting dichlorocarbyne complex. Treatment of {ReCl(PMe2 Ph)3 }2 {≡CCH=C(CMe3 )C≡C-}2 with HCl produced the dichloro-rhenium carbyne complex Re{≡CCH=C(CMe3 )C≡CH}Cl2 (PMe2 Ph)3 , which is consistent with the electronic structure of the 12-membered metallacycles.