Alkylation of iridium 5,10,15,20-tetrakistolylporphyrinato carbonyl chloride, Ir(ttp)Cl(CO) (1), with 1°, 2° alkyl halides was achieved to give (ttp)Ir-alkyls in good yields under air and water compatible conditions by utilizing KOH as the cheap reducing agent. The reaction rate followed the order: RCl < RBr < RI (R = alkyl), and suggests an SN2 pathway by [Ir(I)(ttp)](-). Ir(ttp)-adamantyl was obtained under N2 when 1-bromoadamantane was utilized, which could only undergo bromine atom transfer pathway. Mechanistic investigations reveal a substrate dependent pathway of SN2 or halogen atom transfer.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/c5dt03845f | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Dinitrogen Activation: A Novel Approach with P/B Intermolecular FLP.
J Phys Chem A
January 2025
School of Applied Science and Humanities, Haldia Institute of Technology, ICARE Complex, Haldia 721657, India.
This study explores the reactivity of a new intermolecular P/B frustrated Lewis pair in the context of dinitrogen activation through a push-pull mechanism. The ab initio molecular dynamics model known as atom-centered density matrix propagation plays a pivotal role in elucidating the weakly associated encounter complex. In-depth analysis, mainly through intrinsic reaction coordinate calculations, supports a single-step mechanism.
View Article and Find Full Text PDFInsights into excitonic behavior in single-atom covalent organic frameworks for efficient photo-Fenton-like pollutant degradation.
Nat Commun
January 2025
Department of Environment, Zhejiang University of Technology, Hangzhou, 310014, China.
The generation of radicals through photo-Fenton-like reactions demonstrates significant potential for remediating emerging organic contaminants (EOCs) in complex aqueous environments. However, the excitonic effect, induced by Coulomb interactions between photoexcited electrons and holes, reduces carrier utilization efficiency in these systems. In this study, we develop Cu single-atom-loaded covalent organic frameworks (Cu/COFs) as models to modulate excitonic effects.
View Article and Find Full Text PDFNon-metallic iodine single-atom catalysts with optimized electronic structures for efficient Fenton-like reactions.
Nat Commun
January 2025
State Environmental Protection Key Laboratory of Environmental Health Impact Assessment of Emerging Contaminants, School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai, P.R. China.
In this study, we introduce a highly effective non-metallic iodine single-atom catalyst (SAC), referred to as I-NC, which is strategically confined within a nitrogen-doped carbon (NC) scaffold. This configuration features a distinctive C-I coordination that optimizes the electronic structure of the nitrogen-adjacent carbon sites. As a result, this arrangement enhances electron transfer from peroxymonosulfate (PMS) to the active sites, particularly the electron-deficient carbon.
View Article and Find Full Text PDFAssembly-foaming synthesis of hierarchically porous nitrogen-doped carbon supported single-atom iron catalysts for efficient oxygen reduction.
J Colloid Interface Sci
January 2025
Particle Engineering Laboratory (China Petroleum and Chemical Industry Federation), School of Chemical and Environmental Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 Jiangsu, PR China. Electronic address:
High-performance electrocatalysts are highly concerned in oxygen reduction reaction (ORR) related energy applications. However, facile synthesis of hierarchically porous structures with highly exposed active sites and improved mass transfer is challenging. Herein, we develop a novel assembly-foaming strategy for synthesizing hierarchically porous nitrogen-doped carbon supported single-atom iron catalysts.
View Article and Find Full Text PDFApplication of modern artificial intelligence techniques in the development of organic molecular force fields.
Phys Chem Chem Phys
January 2025
Institute of Materials Research (IMR), Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, 518055, China.
The molecular force field (FF) determines the accuracy of molecular dynamics (MD) and is one of the major bottlenecks that limits the application of MD in molecular design. Recently, artificial intelligence (AI) techniques, such as machine-learning potentials (MLPs), have been rapidly reshaping the landscape of MD. Meanwhile, organic molecular systems feature unique characteristics, and require more careful treatment in both model construction, optimization, and validation.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!