Organic cage-anchored ultrafine palladium nanoparticles enable direct C(sp2)–H arylation of benzothiazole
- 1Department of Chemistry, Guru Ghasidas Vishwavidyalaya Koni Bilaspur-495009 Chhattisgarh India
- 2Department of Physics and Astrophysics, University of Delhi Delhi 110007 India
Abstract
Controlled synthesis of ultrafine palladium nanoparticles (Pd NPs) remains a significant challenge, as their high surface energy often leads to rapid aggregation, reducing catalytic activity and stability. Here, we report a cryptand-like porous organic amine cage as a template as well as stabilizer for the fabrication of ultrafine Pd NPs. The cage was synthesized through imine condensation of terephthaldehyde with tris(2-aminoethyl)amine, followed by reductive amination, affording a robust amine-linked cryptand (PAC) with multiple coordination sites. Subsequent addition of Pd(OAc)2, followed by the in situ reduction, generated well-dispersed Pd NPs (size ∼4 nm) confined within the intermolecular cage space as evident from FT-IR, UV-vis and BET surface area analyses. The hybrid PAC-supported Pd nanomaterial (Pd/PAC) was comprehensively characterised by using multiple analytical techniques UV-vis, FT-IR, BET, PXRD, FE-SEM, HR-TEM, and XPS. The Pd/PAC hybrid catalyst efficiently promotes the direct C(sp2)–H arylation of benzothiazole with haloarenes, affording diverse 2-aryl benzothiazole derivatives in moderate to excellent yields (72–85%) with a broad substrate scope, with excellent recyclability up to 6 cycles with no Pd leaching as evident from ICP-MS analysis of the filtrate under hot conditions. Further, DLS study of the reaction mixture confirms the retention of the particulate nature of Pd NPs during the course of the reaction, indicating the heterogenous behavour of the catalyst. Moreover, mechanistic insights were obtained through DFT analysis, which supported a plausible pathway involving oxidative addition and reductive elimination during the catalytic cycle. Notably, to the best of our knowledge, this study presents the first example of an organic cage-stabilized palladium nanoparticle-catalyzed C–H activation of benzothiaozole.
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BibTeX
@article{deshmukh2026organic,
title = {{Organic cage-anchored ultrafine palladium nanoparticles enable direct C(sp2)–H arylation of benzothiazole}},
author = {Muskan Deshmukh and Kumari Anchal and Kumkum Priyadarshini Sahu and Pallab Bhandari and Bijnaneswar Mandal and Sevi Murugavel and Subhash Banerjee},
journal = {RSC advances},
year = {2026},
month = oct,
doi = {10.1039/d6ra06468j},
url = {https://europepmc.org/article/PMC/PMC13670041},
note = {CC BY-NC},
}
RIS
TY - JOUR
TI - Organic cage-anchored ultrafine palladium nanoparticles enable direct C(sp2)–H arylation of benzothiazole
AU - Muskan Deshmukh
AU - Kumari Anchal
AU - Kumkum Priyadarshini Sahu
AU - Pallab Bhandari
AU - Bijnaneswar Mandal
AU - Sevi Murugavel
AU - Subhash Banerjee
PY - 2026
DA - 2026/10/15
JO - RSC advances
DO - 10.1039/d6ra06468j
UR - https://europepmc.org/article/PMC/PMC13670041
AB - Controlled synthesis of ultrafine palladium nanoparticles (Pd NPs) remains a significant challenge, as their high surface energy often leads to rapid aggregation, reducing catalytic activity and stability. Here, we report a cryptand-like porous organic amine cage as a template as well as stabilizer for the fabrication of ultrafine Pd NPs. The cage was synthesized through imine condensation of terephthaldehyde with tris(2-aminoethyl)amine, followed by reductive amination, affording a robust amine-linked cryptand (PAC) with multiple coordination sites. Subsequent addition of Pd(OAc)2, followed by the in situ reduction, generated well-dispersed Pd NPs (size ∼4 nm) confined within the intermolecular cage space as evident from FT-IR, UV-vis and BET surface area analyses. The hybrid PAC-supported Pd nanomaterial (Pd/PAC) was comprehensively characterised by using multiple analytical techniques UV-vis, FT-IR, BET, PXRD, FE-SEM, HR-TEM, and XPS. The Pd/PAC hybrid catalyst efficiently promotes the direct C(sp2)–H arylation of benzothiazole with haloarenes, affording diverse 2-aryl benzothiazole derivatives in moderate to excellent yields (72–85%) with a broad substrate scope, with excellent recyclability up to 6 cycles with no Pd leaching as evident from ICP-MS analysis of the filtrate under hot conditions. Further, DLS study of the reaction mixture confirms the retention of the particulate nature of Pd NPs during the course of the reaction, indicating the heterogenous behavour of the catalyst. Moreover, mechanistic insights were obtained through DFT analysis, which supported a plausible pathway involving oxidative addition and reductive elimination during the catalytic cycle. Notably, to the best of our knowledge, this study presents the first example of an organic cage-stabilized palladium nanoparticle-catalyzed C–H activation of benzothiaozole.
SN - 2046-2069
ER -