14‐Vertex Heteroboranes with 14 Skeletal Electron Pairs: An Experimental and Computational Study. (2nd June 2016)

• Record Type: Journal Article
• 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.
• Is Part Of: Angewandte Chemie. Volume 128:Number 30(2016)
• Page Start: 8848
• Page End: 8852
• Publication Date: 2016-06-02
• Subjects: Carborane -- Dichtefunktionalrechnungen -- Käfigverbindungen -- Ruthenium -- Strukturaufklärung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201602440
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Three isomers of [(Cp*Ru)2 C2 B10 H12 ], 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‐RuC2 B10 H12 ] − . 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 11 B and 1 H 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.