Triple Frustrated Lewis Pair-Type Reactivity on a Single Rare-Earth Metal Center.

Chemistry

State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P. R. China.

Published: April 2020

Rare-earth metal cations have been used rarely as Lewis-acidic components in the chemistry of frustrated Lewis pairs (FLPs). Herein, we report the first cerium/phosphorus system (2) employing a heptadentate N P ligand, which exhibits triple FLP-type reactivity towards a series of organic substrates, including isocyanates, isothiocyanates, diazomethane, and azides on a single rare-earth Lewis acidic Ce center. This result shows that the Ce center and three P atoms in 2 could simultaneously activate three equivalents of small molecules under mild conditions. This study broadens the diversity of FLPs and demonstrates that rare earth based FLP exhibit unique properties compared with other FLP systems.

Download full-text PDF

Source
http://dx.doi.org/10.1002/chem.201905629DOI Listing

Publication Analysis

Top Keywords

frustrated lewis
8
single rare-earth
8
rare-earth metal
8
triple frustrated
4
lewis pair-type
4
pair-type reactivity
4
reactivity single
4
metal center
4
center rare-earth
4
metal cations
4

Similar Publications

This article aims to examine the lived experiences of attention-deficit/hyperactivity disorder (ADHD) diagnosis in adulthood, emphasising its revelatory nature and diverse emotional responses it provokes. The diagnosis serves as a pivotal moment of self-discovery, often evoking feelings of validation and identity affirmation. However, it also triggers a complex array of emotions, including grieving for the childhood self, frustration with society's failure to recognise the legitimate challenges and evolving self-concept post diagnosis.

View Article and Find Full Text PDF

Constructing Atomic Tungsten-Based Solid Frustrated-Lewis-Pair Sites with d-p Interactions for Selective CO Photoreduction.

J Am Chem Soc

December 2024

State Key Laboratory of Fluorine & Nitrogen Chemicals, School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an, Shaanxi 710049, China.

Solid frustrated Lewis pair (FLP) shows remarkable advantages in the activation of small molecules such as CO, owing to the strong orbital interactions between FLP sites and reactant molecules. However, most of the currently constructed FLP sites are randomly distributed and easily reunited on the surface of catalysts, resulting in a low utilization rate of FLP sites. Herein, atomic tungsten-based FLP (N···W FLP) sites are constructed for photocatalytic CO conversion through introducing W single-atoms into polymeric carbon nitride.

View Article and Find Full Text PDF

Computational Study of Electrochemical CO Reduction on 2D Graphitic Carbon Nitride Supported Single-Atom (Al and P) Catalysts (SACs).

Chemphyschem

December 2024

Department of Nanoscience, Joint School of Nanoscience & Nanoengineering (JSNN), University of North Carolina at Greensboro, Greensboro, NC 27401, USA.

To mitigate the adverse effects of CO emissions, CO electroreduction to small organic products is a preferable solution and potential catalysts include the single-atom catalyst (SAC) which comprises individual atoms dispersed on 2D materials. Here, we used aluminum and phosphorus as the active sites for CO electroreductions by embedding them on the 2D graphitic carbon nitride (g-CN) nano-surface. The resulting M-CN (M=Al and P) SACs were computationally studied for the CO electroreduction using density functional theory (DFT) and ab-initio molecular dynamics (AIMD) simulations.

View Article and Find Full Text PDF

Surface frustrated Lewis pairs in titanium nitride enable gas phase heterogeneous CO photocatalysis.

Nat Commun

December 2024

State Key Laboratory for Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai, China.

Gas-phase heterogeneous catalytic CO hydrogenation to commodity chemicals and fuels via surface frustrated Lewis pairs is a growing focus of scientific and technological interest. Traditional gas-phase heterogeneous surface frustrated Lewis pair catalysts primarily involve metal oxide-hydroxides (MOH•••M). An avenue to improve the process performance metrics lies in replacing the Lewis base MOH with a stronger alternative; an intriguing example being the amine MNH in metal nitrides.

View Article and Find Full Text PDF

Boron and Oxygen Dual-Doped Carbon Nitride Nanotubes with Frustrated Lewis Pairs for Efficient Electrocatalytic Ammonia Synthesis.

Small Methods

December 2024

Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Jiangsu Province Key Laboratory of Green Biomass-based Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry University, Nanjing, Jiangsu, 210037, China.

This work reports boron and oxygen dual-doped carbon nitride nanotubes (B/O-CNNTs) prepared via a copolymerization process for electrocatalytic ammonia synthesis from nitrogen gas (NRR) and nitrate (NORR) sources, respectively. By adjusting the dosage of boron oxide precursor, the texture and content of B/O dual dopants and the coordination environment in the resulting 1D CNNTs can be tuned. The best B/O-CNNTs can achieve maximum Faradaic efficiencies of 35% and 96% at -1.

View Article and Find Full Text PDF

Want 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!