Nickel coordination compounds featuring Ni-O bonds are key structural motifs in both bioinorganic and synthetic chemistries. They serve as precursors for organic substrate oxidation and are commonly invoked intermediates in water oxidation and oxygen reduction schemes. Herein, we disclose a series of well-defined dinuclear nickel complexes that, upon treatment with CO and HO, afford the first nickel-bound peroxycarbonate. This unprecedented nickel-oxygen intermediate is stabilized by hydrogen bonding templated across the bimetallic core. Contrasting copper and iron analogues, the nickel peroxycarbonate reversibly dissociates HO, a process that is shown to be accelerated by exogenous CO.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/d4cc02241f | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
From a P-Bridging Phosphaketene to μ-Phosphinidenide and μ-Diphosphaurea Units at a Dinickel Core.
Chemistry
November 2024
Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, D-37077, Göttingen, Germany.
Salt metathesis of dinickel(II) complex LNiBr (1; L is a dinucleating pyrazolate ligand with two β-diketiminato chelate arms) with Na(OCP) ⋅ (dioxane) yielded LNi(PCO) (2) with a P-bridging phosphaethynolate. Further reaction of 2 with benzyl isocyanide or with an N-heterocyclic carbene (NHC) triggered decarbonylation and gave LNi(PCN-CHPh) (3) and LNiP(NHC) (4) with P-bridging cyanophosphide and NHC-phosphinidenide, respectively. Electronic structure analysis indicated a μ-η : η binding mode of the PCO anion between the two Ni ions in 2, which is even more pronounced for the [PCN(-CHPh)] anion in 3.
View Article and Find Full Text PDFExploring the conformational space of the mobile flap in Sporosarcina pasteurii urease by cryo-electron microscopy.
Int J Biol Macromol
December 2024
Department of Agricultural, Food and Environmental Sciences, Polytechnic University of Marche, I-60131 Ancona, Italy. Electronic address:
To fully understand enzymatic dynamics, it is essential to explore the complete conformational space of a biological catalyst. The catalytic mechanism of the nickel-dependent urease, the most efficient enzyme known, holds significant relevance for medical, pharmaceutical, and agro-environmental applications. A critical aspect of urease function is the conformational change of a helix-turn-helix motif that covers the active site cavity, known as the mobile flap.
View Article and Find Full Text PDFGram-Scale, One-Pot Synthesis of a Cofacial Porphyrin Bridged by Ortho-xylene as a Scaffold for Dinuclear Architectures.
Inorg Chem
November 2024
Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York14260, United States.
Herein, we report the reaction between four 1,2-dibromoxylenes and two tetra-3-pyridylporphyrins for the formation of a cofacial porphyrin core spanned by dipyridinium xylene moieties. The metal-free organic nanocage (oNC) was synthesized in one twenty-four h step at a gram-scale with a 91.5% yield.
View Article and Find Full Text PDFUnique Oxygen-Bridged Nickel Atomic Pairs Efficiently Boost Electrochemical Reduction of Carbon Dioxide.
Small
November 2024
State Key Laboratory of Fine Chemicals, Department of Catalysis Chemistry and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024, P. R. China.
Benefiting from the synergism between adjacent bimetallic atoms, in comparison with single atom catalysts, the dual atom catalysts have displayed great potential in electrocatalytic CO reduction reaction (CORR). However, the further modulation of the electronic structure of dual atom sites to enhance CORR performance still remains a challenge. Herein, an atomically dispersed oxygen-bridged NiNO/NC catalyst with unique Ni-O-Ni sites is successfully synthesized through the microwave pyrolysis of the supported mixture containing the dinuclear nickel phthalocyanine and glucose on N-doped carbon nanosheets.
View Article and Find Full Text PDFNi(II) Cylinders Damage DNA in Cancer Cells and Preferentially Bind Y-Shaped DNA Three-Way Junctions Blocking DNA Synthesis.
Small
December 2024
Czech Academy of Sciences, Institute of Biophysics, Brno, CZ-61200, Czech Republic.
Article Synopsis
- DNA three-way junctions play a crucial role in biological processes and can be used in disease treatment; this study focuses on how specific nickel cylinders interact with these junctions.
- The nickel cylinders demonstrated a strong preference for binding to Y-shaped DNA three-way junctions even when faced with competing DNA structures, effectively halting DNA synthesis by stabilizing the junctions on the template strand.
- Additionally, the study found that these cylinders can cause DNA damage in cancer cells, leading to double-strand breaks, which suggests potential therapeutic implications and risks associated with their use.
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!