Department of Applied Chemistry, Tokyo University of Science,1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
Published: July 2024
AI Article Synopsis
Article Abstract
Amidst burgeoning interest, atomically precise copper nanoclusters (Cu NCs) have emerged as a remarkable class of nanomaterials distinguished by their unparalleled reactivity. Nonetheless, the synthesis of hydride-free Cu NCs and their role as stable catalysts remain infrequently explored. Here, we introduce a facile synthetic approach to fabricate a hydride-free [Cu(SCH)(PPh)] (Cu) NC and delineate its photophysical properties intertwined with their structural configuration. Moreover, the utilization of its photophysical properties in a photoinduced C-C coupling reaction demonstrates remarkable specificity toward cross-coupling products with high yields. The combined experimental and theoretical investigation reveals a nonradical mechanistic pathway distinct from its counterparts, offering promising prospects for designing hydride-free Cu NC catalysts in the future and unveiling the selectivity of the hydride-free [Cu(SCH)(PPh)] NC in photoinduced Sonogashira C-C coupling through a polar reaction pathway.
Amidst burgeoning interest, atomically precise copper nanoclusters (Cu NCs) have emerged as a remarkable class of nanomaterials distinguished by their unparalleled reactivity. Nonetheless, the synthesis of hydride-free Cu NCs and their role as stable catalysts remain infrequently explored. Here, we introduce a facile synthetic approach to fabricate a hydride-free [Cu(SCH)(PPh)] (Cu) NC and delineate its photophysical properties intertwined with their structural configuration.
Institute of Inorganic Chemistry and Center for Sustainable Systems Design (CSSD), Paderborn University, Warburger Straße 100, 33098, Paderborn, Germany.
Transition metal complexes, particularly copper hydrides, play an important role in various catalytic processes and molecular inorganic chemistry. This study employs synchrotron hard X-ray spectroscopy to gain insights into the geometric and electronic properties of copper hydrides as potential catalysts for CO hydrogenation. The potential of high energy resolution X-ray absorption near-edge structure (HERFD-XANES) and valence-to-core X-ray emission (VtC-XES) is demonstrated with measurement on Stryker's reagent (CuH) and [Cu(μ-H)(dpmppe)](PF) (CuH), alongside a non-hydride copper compound ICu(dtbppOH) (Cuy-I).
Hydrogenation reactions of carbon-carbon unsaturated bonds are central in synthetic chemistry. Efficient catalysis of these reactions classically recourses to heterogeneous or homogeneous transition-metal species. Whether thermal or electrochemical, C-C multiple bond catalytic hydrogenations commonly involve metal hydrides as key intermediates.
Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, 30 Marie Curie, University of Ottawa, Ottawa, ON K1N 6N5 Canada.
ConspectusHomogeneous catalysis is at the forefront of global efforts to innovate the synthesis of fine chemicals and achieve carbon-neutrality in energy applications. For decades, the push toward sustainable catalysis has focused on the development of first-row transition metal catalysts to supplant widespread use of precious metals. Metal-ligand cooperativity is an effective strategy to yield high-performing first-row metal molecular catalysts.
A transition metal- and hydride-free protocol has been developed for the chemoselective reduction of α-keto esters and α-keto amides using rongalite as a reducing agent. Here, rongalite acts as a hydride-free reducing agent a radical mechanism. This protocol offers the synthesis of a wide range of α-hydroxy esters and α-hydroxy amides with 85-98% yields.
