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The synthesis and structural characterization of new derivatives of [B
H
]
is of fundamental interest and is expected to allow for extended applications. Herein we report on the synthesis of a series of amidine, amide, urea and isocyanate derivatives based on the amino-
-dodecaborate anion [B
H
NH₃]
. Their structures have been confirmed by spectroscopic methods, and nine crystal structures are presented.