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The first cationic main grouptetrahydroborate complexes are reported. [Ca(BH4)(THF)5][BPh4] and the charge neutral (TptBu,Me)Ca(BH4)(THF) are initiators for the living ring opening polymerization of rac-lactide, the latter producing PLA with high levels of heterotactic enrichment. These represent a new class of ROPinitiators for main group metals.
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