1. What are carboranes?
Give the method of preparation, structure and reactions of
dicarbaclosododecacarboranes.
Carboranes are compounds of carbon, boron and hydrogen where these occupy vertices of
a triangular polyhedron. Here a BH group of a normal borane is substituted with a CH unit.
They are structurally similar to boranes, but shows different characteristics. Carboranes are
classified into 3; closo, nido and arachno type, out of which chemistry of closoboranes are
extensively studied. Closo boranes have same cage geometry as that of BnHn2- and also due
to extensive delocalization of skeletal electrons, it has high thermal and oxidative stability.
One such important closo borane is dicarbaclosododecacarborane.
Dicarbaclosododecacarborane
Dicarbaclosododecacarborane has a closed icosahedral structure. It occurs in three isomeric
forms, viz. ortho, meta and para. All three isomers are quite stable in air and can be easily
prepared from B10H14. Decaborane on reaction with thioether, Et2S forms a compound
which on reaction with acetylene yields ortho isomer of dicarbaclosododecacarborane. This
compound on further heating above 470oC yields its meta isomer and if heated above 700oC
yields a para isomer. The only change in the isomeric form of this compound is that in
ortho form C atom is at 1,2 position, in meta form it is at 1,7 and in para at 1,12. The
reactions are given below
Heat
B10H14 + 2Et2S → B10H12(Et2S)2 + H2
B10H12(Et2S)2 + CH ≡CH → closo-1,2-C2B10H12 + H2 + 2Et2S
470o C 700o C
closo-1,2-C2B10H12 → 1,7-C2B10H12→ 1,12-C2B10H12
Structure
Reactivity
As a consequence of difference in relatively electronegative atom, the CH protons in these
cages are slightly acidic. In the above case ortho isomer is most acidic. The order becomes
1,2 > 1,7 > 1,12 isomer. These reactive protons can be removed by BuLi, Grignard reagents
resulting in C-mono or C,C’- dilithio derivatives. These derivatives can be converted to
other organosubstituted products.
H2C2B10H10 + 2LiBu → Li2C2B10H10 (Dilithio derivative)
Reactions are given as
I2
Li2C2B10H10 → I2C2B10H10
CO2
Li2C2B10H10 → (COOH)2C2B10H10
H2 O , HCHO
Li2C2B10H10 → (CH2OH)2C2B10H10
NOCl
Li2C2B10H10 → (NO)2C2B10H10
Polyhedral rearrangements
This is another type of reaction given by icosahedral C2B10H12, in which the ortho isomer
on heating above 450oC gives meta isomer, which on further heating above 700 oC yields
para isomer. The mechanism is not yet identified successfully, but is believed to move by
diamond-square-diamond pathway.
2. What are metallocarboranes? How are sandwich type compounds synthesized?
Explain the nature of bonding in such compounds.
Metallocarboranes are metal complexes of carborane anions. They have both metal and
carbon atom in a cage skeleton containing boron and hydrogen. They are much stable than
metallocenes and also tend to stabilize metals of higher oxidation states. E.g.
[Cu(II)1,2-C2B9H11]2- is more stable but cuprocene (corresponding metallocene) is less
stable. They are less reactive to hydrogen, nitrogen, CO or PPh3 as the corresponding
metallocenes do.
Preparation of sandwich compounds
The starting material of metallocarboranes are nido dicarbollide anions formed from
C2B9H12- by the reaction with NaOH. The dicarbollide anion has a pentagonal face. The
reaction is given below.
C2B9H12- + NaOH → C2B9H112- + Na+ + H2
The reaction of dicarbollide anion with FeCl2 in tetrahydrofuran with rigorous exclusion
of moisture and air gives pink, diamagnetic bis-sandwich compound of Fe(II), which can
be easily oxidized to the corresponding red Fe(III) complex.
2C2B9H112- + Fe(II) → [Fe(II)(η5-C2B9H11)2]2- → [Fe(III)(η5-C2B9H11)2]-
If the reaction is carried out in the presence of NaC5H5, the purple mixed complex is
obtained.
C2B9H112- + C5H5- + Fe(II) → [(η5-C5H5) Fe(III)(η5-C2B9H11)]
The reaction is general and can be carried out for any transition metals like Cr, Mo, W, Mn
etc. Sometimes metal carbonyls supply the capping unit.
Other methods of preparation of metallocarboranes include polyhedral expansion,
polyhedral contraction, polyhedral subrogation, thermal metal transfer and direct oxidative
insertion of metallic center.
Bonding and structure
Pink sandwich compound of iron can be taken as an example here.
