Jonathan A. Kephart, Daniel Y. Zhou, Jason Sandwisch, Nathalia Cajiao, Sebastian M. Krajewski, Paul Malinowski, Jiun-Haw Chu, Michael L. Neidig, Werner Kaminsky and Alexandra Velian*,
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引用次数: 0
Abstract
Directing groups guide substitution patterns in organic synthetic schemes, but little is known about pathways to control reactivity patterns, such as regioselectivity, in complex inorganic systems such as bioinorganic cofactors or extended surfaces. Interadsorbate effects are known to encode surface reactivity patterns in inorganic materials, modulating the location and binding strength of ligands. However, owing to limited experimental resolution into complex inorganic structures, there is little opportunity to resolve these effects on the atomic scale. Here, we utilize an atomically precise Fe/Co/Se nanocluster platform, [Fe3(L)2Co6Se8L′6]+ ([1(L)2]+; L = CNtBu, THF; L′ = Ph2PN(−)Tol), in which allosteric interadsorbate effects give rise to pronounced site-differentiation. Using a combination of spectroscopic techniques and single-crystal X-ray diffractometry, we discover that coordination of THF at the ligand-free Fe site in [1(CNtBu)2]+ sets off a domino effect wherein allosteric through-cluster interactions promote the regioselective dissociation of CNtBu at a neighboring Fe site. Computational analysis reveals that this active site correlation is a result of delocalized Fe···Se···Co···Se covalent interactions that intertwine edge sites on the same cluster face. This study provides an unprecedented atom-scale glimpse into how interfacial metal–support interactions mediate a collective and regiospecific path for substrate exchange across multiple active sites.
Akin to directing groups in organic chemistry, allostery directs reaction chemistry across multiple active sites at the surface of an inorganic cluster.
期刊介绍:
ACS Central Science publishes significant primary reports on research in chemistry and allied fields where chemical approaches are pivotal. As the first fully open-access journal by the American Chemical Society, it covers compelling and important contributions to the broad chemistry and scientific community. "Central science," a term popularized nearly 40 years ago, emphasizes chemistry's central role in connecting physical and life sciences, and fundamental sciences with applied disciplines like medicine and engineering. The journal focuses on exceptional quality articles, addressing advances in fundamental chemistry and interdisciplinary research.