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The sequence of electrophilic substitution for o- and m-carborane has been the subject of much experimental and theoretical work. The molecular structure of tribromo-m-carborane (m-B10Br3H7C2H2) shows that the third bromine atom to be substituted is found bonded to boron atom 12 (or 5). The crystal data are: space group, Pbcm; a = 8.47(4), b = 12.19(8), and c = 12.25(8) Å; ρo = 1.98(2) and ρc = 2.00 g/cm3 for Z = 4. Data were collected using Weissenberg geometry and Ni-filtered CuK, radiation. The visually estimated intensities of 920 reflections were used in the anisotropic block-diagonalized least-squares refinement of the 76 structural parameters. The final value of the conventional residual index was 0.087.

(Herstellung der Titelverbindung als Chlorbenzol‐Solvat aus (η5‐C5H5)2ZrC12 und wasserfreiem Na‐dimethyldithiocarbamat.

Beim Behandeln des Di‐Li‐Addukts von 1,2‐Dicarba‐closo‐dodekaboran(12) in Äther mit einem Äquivalent (Ph3P)2NiCl2 (Ph = ‐C6H5) in Äther entsteht der Komplex (Ph3P)2NiC2B10H10, für den aufgrund von analytischen, IR‐ und NMR‐Daten eine Struktur mit o‐Bindungen zwischen dem Ni‐Atom und den beiden C‐Atomen der chelatbildenden o‐Carboran‐Einheit diskutiert wird.