In this Comment, we suggest salt metathesis (or ion exchange) as an ultimate click reaction, extending click chemistry principles beyond covalent bonds to ionic interactions. These universal and robust reactions, which nature utilizes in marine organisms' biomineralization processes, proceed spontaneously under mild conditions with minimal waste, embodying the core principles of click philosophy. This perspective expands the traditional scope of click chemistry and opens new opportunities in synthetic accessibility across organic, inorganic, and materials science spaces.
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http://dx.doi.org/10.1021/prechem.4c00088 | DOI Listing |
J Am Chem Soc
March 2025
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, School of Chemistry, IGCME, Sun Yat-sen University, Guangzhou 510275, China.
Nitroso compounds, R-N═O, containing N═O double bonds are ubiquitous and widely utilized in organic synthesis. In contrast, heavier congeners of nitroso compounds, namely pnictinidene chalcogenides R-Pn = E (Pn = P, As, Sb, Bi; E = O, S, Se, Te), are highly reactive and scarce. They have been stabilized in the coordination sphere of Lewis acid/base or by pronounced contribution from resonance structures, whereas free species with unperturbed pnictogen-chalcogen double bonds remains elusive.
View Article and Find Full Text PDFJ Am Chem Soc
March 2025
Center for Catalysis Research and Innovation, and Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
The metathetical modification of biomolecules in aqueous environments holds great promise for advances at the interface of chemistry, biology, and medicine. However, rapid degradation of the metathesis catalysts necessitates their use in large stoichiometric excess, resulting in undesired side-reactions promoted by the ruthenium products. Although water is now known to play a central role in catalyst decomposition, the elusive nature of the intermediates has hampered insight into the pathways involved.
View Article and Find Full Text PDFChem Commun (Camb)
March 2025
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India.
Herein, we report an unprecedented NHC ligand substitution around a ruthenium center, exploiting an orthometalated complex. Captivatingly, the employed metal complex here undergoes a unique σ-bond metathesis in the presence of an alkene and azolium salt, leading to facile exchange of ancillary NHC ligands at the Ru-center, which is not known to the best of our knowledge.
View Article and Find Full Text PDFPrecis Chem
February 2025
Department of Chemistry, State University of New York at Oswego, Oswego, New York 13126, United States.
In this Comment, we suggest salt metathesis (or ion exchange) as an ultimate click reaction, extending click chemistry principles beyond covalent bonds to ionic interactions. These universal and robust reactions, which nature utilizes in marine organisms' biomineralization processes, proceed spontaneously under mild conditions with minimal waste, embodying the core principles of click philosophy. This perspective expands the traditional scope of click chemistry and opens new opportunities in synthetic accessibility across organic, inorganic, and materials science spaces.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
February 2025
TUM School of Natural Sciences, Department of Chemistry, Catalysis Research Center and Institute of Silicon Chemistry, Technical University of Munich, Garching bei München, Germany.
This work explores the use of plumbylene-phosphinidenes to address the challenge of isolating P=Pb bonds. Herein, we report the synthesis of three N-heterocyclic carbene phosphinidene (NHCP) substituted chlorotetrylene dimers [(IDipp)PECl] (E=Ge, Sn, Pb; IDipp=C([N-(2,6-Pr-CH)CH])). Substituent attachment via salt metathesis (E=Sn, Pb) enables the isolation of NHCP-silyl-substituted stannylene (IDipp)PSn(SiTmsSiTol) as well as NHCP-silyl- and NHCP-aryl-substituted plumbylenes (IDipp)PPb(SiTmsSiTol) and (IDipp)PPb(Ter) (Ter=2,6-MesCH, Tms=Trimethylsilyl).
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