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ChemRxiv219.pdf (8 MB)
Hydrolysis of Scandium Alkyl Derivatives Supported by a Pentadentate Diborate Ligand: Interconversion of Hydroxo and Oxo Complexes
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submitted on 10.12.2019 and posted on 17.12.2019by Daniel W. Beh, Warren Piers, Laurent Maron, Yan Yang, Benjamin
S. Gelfand, Jian-Bin Li
reaction of water with scandium alkyls (compounds 1-R) supported by a dianionic, pentadentate ligand leads to rapid
formation of an oxo-bridged dimer (2).
Solid state samples can be exposed to ambient atmosphere to generate samples
enriched in the bridging dihydroxo dimer 3,
which slowly converts to the m-oxo species with elimination of water. DFT computations show that 3 is actually more thermodynamically
stable than 2, but the reactivity of
3 with the water eliminated leads to
its decomposition to 2 and several
hydrolysis products. Some of these products were characterized by X-ray crystallography,
specifically a hexameric scandium dihydroxo cluster (4) in which the pentadentate ligand has partially demetallated.
Attempts to synthesize hydroxo complex 3
by protonation of 2 also lead to