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Isomerization of Na‐Centered Alkyltin Keggin Clusters
Author(s) -
Hutchison Danielle C.,
Smith Rachelle M.,
Nyman May
Publication year - 2021
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000880
Subject(s) - chemistry , lability , isomerization , cluster (spacecraft) , polyoxometalate , crystallography , nuclear magnetic resonance spectroscopy , tungsten , keggin structure , spectroscopy , catalysis , stereochemistry , organic chemistry , physics , quantum mechanics , computer science , programming language
The Keggin cluster topology, discovered in tungsten polyoxometalates approximately a century ago, is now broadly represented across the periodic table. The alkyltin Keggin clusters are unique in that it is the only Keggin family that appears to favor the rarer β and γ rotational isomers, co‐crystallized as β,γ‐[(BuSn) 12 (NaO 4 )(OCH 3 ) 12 (O) 5 (OH) 7 ] (β,γ‐NaSn 12 ). Nuclear Magnetic Resonance Spectroscopy (NMR; 1 H, 119 Sn) studies show lability and ready exchange between hydroxy‐methoxy ligands, accelerated by residual water in polar solvents. Room temperature and heated solutions of β,γ‐NaSn 12 show five distinct 23 Na NMR peaks, corresponding to all five of the Keggin rotational isomers simultaneously in solution. This is the only example of coexistence of all Keggin isomers simultaneously, providing more in‐depth insight into parameters influencing Keggin isomer stabilization, isolation, and exchange.