14-Vertex Heteroboranes with 14 Skeletal Electron Pairs: An Experimental and Computational Study

• Published in: Angewandte Chemie International Edition 2016-07, Vol.55 (30), p.8706-8710
• Main Authors: Robertson, Alasdair P. M., Beattie, Nicholas A., Scott, Greig, Man, Wing Y., Jones, John J., Macgregor, Stuart A., Rosair, Georgina M., Welch, Alan J.
• Format: Article
• Language: English
• Subjects: cage compounds; carboranes; density functional calculations; Electrons; ruthenium; structure elucidation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201602440

Three isomers of [(Cp*Ru)2C2B10H12], the first examples of 14‐vertex heteroboranes containing 14‐skeletal electron pairs, have been synthesized by the direct electrophilic insertion of a {Cp*Ru+} fragment into the anion [4‐Cp*‐4,1,6‐RuC2B10H12]−. All three compounds have the same unique polyhedral structure having an approximate Cs symmetry and featuring a four‐atom trapezoidal face. X‐ray diffraction studies could confidently identify only one of the two cage C atoms in each structure. The other C atom position has been established by a combination of i) best fitting of computed and experimental 11B and 1H NMR chemical shifts, and ii) consideration of the lowest computed energy for series of isomers studied by DFT calculations. In all three isomers, one cage C atom occupies a degree‐4 vertex on the short parallel edge of the trapezium. Living on the edge: The first three examples of 14‐vertex heteroboranes with 14 skeletal electron pairs have been prepared and characterized by a combination of spectroscopic, crystallographic, and computational techniques. The compounds [(Cp*Ru)2C2B10H12] all share a unique cluster structure featuring a trapezoidal face. Atom colors: C gray, B yellow, Ru blue.