Replacement of B-H hydrogen atoms with Cl or Br facilitates the previously unknown oxidative conversion of a nido- to a closo-6-vertex metallacarborane [Eq. (1); X=Cl, Br]. Oxidative cage closure, separation of carbon atoms upon thermal rearrangement, reductive cage opening, and cage expansion by boron insertion have all been applied to a single system, to afford synthetic access to new cluster types.
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