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Coordinatively Unsaturated Metallates of Cobalt(II), Nickel(II), and Zinc(II) Guarded by a Rigid and Narrow Void

[Image: see text] Both natural enzymatic systems and synthetic porous material catalysts utilize well-defined and uniform channels to dictate reaction selectivities on the basis of size or shape. Mimicry of this design element in homogeneous systems is generally difficult owing to the flexibility in...

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Autores principales: Hastings, Christopher D., Huffman, Lucy S. X., Tiwari, Chandan Kumar, Betancourth, Jolaine Galindo, Brennessel, William W., Barnett, Brandon R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10394664/
https://www.ncbi.nlm.nih.gov/pubmed/37462947
http://dx.doi.org/10.1021/acs.inorgchem.3c01335
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author Hastings, Christopher D.
Huffman, Lucy S. X.
Tiwari, Chandan Kumar
Betancourth, Jolaine Galindo
Brennessel, William W.
Barnett, Brandon R.
author_facet Hastings, Christopher D.
Huffman, Lucy S. X.
Tiwari, Chandan Kumar
Betancourth, Jolaine Galindo
Brennessel, William W.
Barnett, Brandon R.
author_sort Hastings, Christopher D.
collection PubMed
description [Image: see text] Both natural enzymatic systems and synthetic porous material catalysts utilize well-defined and uniform channels to dictate reaction selectivities on the basis of size or shape. Mimicry of this design element in homogeneous systems is generally difficult owing to the flexibility inherent in most small molecular species. Herein, we report the synthesis of a tripodal ligand scaffold that orients a narrow and rigid cavity atop accessible metal coordination space. The permanent void is formed through a macrocyclization reaction whereby the 3,5-dihydroxyphenyl arms are covalently linked through methylene bridges. Deprotonative metallation leads to anionic and coordinatively unsaturated complexes of divalent cobalt, nickel, and zinc. An analogous series of trigonal monopyramidal complexes bearing a nonmacrocyclized variant of the tripodal ligand are also reported. Physical characterization of the coordination complexes has been carried out using multiple spectroscopic techniques (NMR, EPR, and UV–vis), cyclic voltammetry, and X-ray diffraction. Complexes of the macrocyclized [L(OCH2O)](3–) ligand retain a rigid cavity upon metallation, with this cavity guarding the entrance to the open axial coordination site. Through a combination of spectroscopic and computational studies, it is shown that acetonitrile entry into the void is sterically precluded, disrupting anticipated coordination at the intracavity site.
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spelling pubmed-103946642023-08-03 Coordinatively Unsaturated Metallates of Cobalt(II), Nickel(II), and Zinc(II) Guarded by a Rigid and Narrow Void Hastings, Christopher D. Huffman, Lucy S. X. Tiwari, Chandan Kumar Betancourth, Jolaine Galindo Brennessel, William W. Barnett, Brandon R. Inorg Chem [Image: see text] Both natural enzymatic systems and synthetic porous material catalysts utilize well-defined and uniform channels to dictate reaction selectivities on the basis of size or shape. Mimicry of this design element in homogeneous systems is generally difficult owing to the flexibility inherent in most small molecular species. Herein, we report the synthesis of a tripodal ligand scaffold that orients a narrow and rigid cavity atop accessible metal coordination space. The permanent void is formed through a macrocyclization reaction whereby the 3,5-dihydroxyphenyl arms are covalently linked through methylene bridges. Deprotonative metallation leads to anionic and coordinatively unsaturated complexes of divalent cobalt, nickel, and zinc. An analogous series of trigonal monopyramidal complexes bearing a nonmacrocyclized variant of the tripodal ligand are also reported. Physical characterization of the coordination complexes has been carried out using multiple spectroscopic techniques (NMR, EPR, and UV–vis), cyclic voltammetry, and X-ray diffraction. Complexes of the macrocyclized [L(OCH2O)](3–) ligand retain a rigid cavity upon metallation, with this cavity guarding the entrance to the open axial coordination site. Through a combination of spectroscopic and computational studies, it is shown that acetonitrile entry into the void is sterically precluded, disrupting anticipated coordination at the intracavity site. American Chemical Society 2023-07-18 /pmc/articles/PMC10394664/ /pubmed/37462947 http://dx.doi.org/10.1021/acs.inorgchem.3c01335 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Hastings, Christopher D.
Huffman, Lucy S. X.
Tiwari, Chandan Kumar
Betancourth, Jolaine Galindo
Brennessel, William W.
Barnett, Brandon R.
Coordinatively Unsaturated Metallates of Cobalt(II), Nickel(II), and Zinc(II) Guarded by a Rigid and Narrow Void
title Coordinatively Unsaturated Metallates of Cobalt(II), Nickel(II), and Zinc(II) Guarded by a Rigid and Narrow Void
title_full Coordinatively Unsaturated Metallates of Cobalt(II), Nickel(II), and Zinc(II) Guarded by a Rigid and Narrow Void
title_fullStr Coordinatively Unsaturated Metallates of Cobalt(II), Nickel(II), and Zinc(II) Guarded by a Rigid and Narrow Void
title_full_unstemmed Coordinatively Unsaturated Metallates of Cobalt(II), Nickel(II), and Zinc(II) Guarded by a Rigid and Narrow Void
title_short Coordinatively Unsaturated Metallates of Cobalt(II), Nickel(II), and Zinc(II) Guarded by a Rigid and Narrow Void
title_sort coordinatively unsaturated metallates of cobalt(ii), nickel(ii), and zinc(ii) guarded by a rigid and narrow void
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10394664/
https://www.ncbi.nlm.nih.gov/pubmed/37462947
http://dx.doi.org/10.1021/acs.inorgchem.3c01335
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