Molecular Rods Combining <i>o</i>‑Carborane and Bicyclo[1.1.1]pentane Cages: An Insertion of the Triple Bond Located Next to a Highly Strained Cage

Octacarbonyl dicobalt and bis­(dimethyl sulfide)­decaborane B₁₀H₁₂(Me₂S)₂ were successfully added to 1,3-diethynylbicyclo[1.1.1]­pentane in good yields. This is an interesting example of a cycloaddition reaction achieved next to the bicyclopentane cage that tends to rearrange in many other cases. It proves that both reagents attack the triple bond in a more or less concerted manner that prevents the rearrangement. Products of the latter reaction are of a particular interest because the bicyclopentane and <i>o</i>-carborane cages are immediately linked in their rodlike structures. The new kind of molecular rotors was thus constructed. ¹H and ¹³C nuclear magnetic resonance spectra in solution reveal an averaged rotational symmetry of the molecules with a well-defined geometry that has been confirmed by X-ray structural analysis in several examples

Molecular Rods Combining <i>o</i>‑Carborane and Bicyclo[1.1.1]pentane Cages: An Insertion of the Triple Bond Located Next to a Highly Strained Cage

Octacarbonyl dicobalt and bis­(dimethyl sulfide)­decaborane B₁₀H₁₂(Me₂S)₂ were successfully added to 1,3-diethynylbicyclo[1.1.1]­pentane in good yields. This is an interesting example of a cycloaddition reaction achieved next to the bicyclopentane cage that tends to rearrange in many other cases. It proves that both reagents attack the triple bond in a more or less concerted manner that prevents the rearrangement. Products of the latter reaction are of a particular interest because the bicyclopentane and <i>o</i>-carborane cages are immediately linked in their rodlike structures. The new kind of molecular rotors was thus constructed. ¹H and ¹³C nuclear magnetic resonance spectra in solution reveal an averaged rotational symmetry of the molecules with a well-defined geometry that has been confirmed by X-ray structural analysis in several examples

Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC–CB₁₁X₁₁^– (X = H, F, CH₃) as Ligands on Pt(II) and Pd(II)

The anionic nitriles 1-R-12-NC–CB₁₁H₁₀^– (R = H, CH₃, I, COOH), 12-NC-1-H–CB₁₁Me₁₀^–, and 12-NC-1-H–CB₁₁F₁₀^– were prepared, and three of them were examined for complex formation with (Et₃P)₂Pt­(II) and (Et₃P)₂Pd­(II). Several stable internally charge-compensated zwitterionic complexes were obtained and characterized. RI-BP86/SV­(P) calculations suggest that their dipole moments exceed 20 D. An attempt to measure the dipole moments in solution failed due to insufficient solubility in solvents of low polarity