A general solution-based
approach to deintercalate zero-valent
tin and copper from two-dimensional layered chalcogenides is presented
using a one-step comproportionation reduction–oxidation reaction.
The reaction is performed between the intercalated zero-valent metal
and high oxidation state metal cations (Sn4+ and Cu2+) dissolved in acetone. This chemistry is shown to work for
a variety of layered chalcogenides with differing morphologies and
crystallinity. Copper and tin are deintercalated from powders of MoS2, MoSe2, NbSe2, and WS2 and
crystalline nanoribbons of Bi2Se3, In2Se3, and GeS. This chemistry achieves a general route
to remove zero-valent tin and copper from 2D layered chalcogenides.
We report the synthesis, characterization, and reactivity of a new low-symmetry β-diketimine featuring a pendant amino(methyl)phenol donor and its corresponding heteroleptic rare-earth (RE) complexes. This includes the first structurally characterized examples of alcoholysis and insertion from an isolated RE III amide in a β-diketimine framework. The flexible methylene linkage leads to RE III complexes with tunable dynamic solution behavior that defines their stoichiometric and catalytic reactivity. The addition of a strong neutral donor ligand, tricyclohexylphosphine oxide, suppresses a prevalent catalyst degradation pathway (base-promoted elimination) and dramatically enhances the catalyst performance in the stereospecific ring-opening polymerization of rac-βbutyrolactone. Our results further demonstrate the importance of ligand reorganization in the stoichiometric and catalytic activity of RE III ions.
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