The synthesis and molecular structure of 3-PPh3- 4-SMe2-3,1,2-closo-CuC2B9H10: Relationship of its structure to those of 10,11-μ-H-9-SMe2-7,8-nido- C2B9H10 and 10,11-μ-(PPh3Au)-9-SMe2-7,8-nido-C2B9H10

Ewan J. M. Hamilton, Alan J. Welch

Research output: Contribution to journalArticle

Abstract

Stoichiometric reaction between Tl[9-SMe2-7,8-nido-C2B9H10] and [Ph3PCuBr]4 affords the title compound in good yield. Crystallographic analysis of this species shows that the copper atom is essentially symmetrically disposed above the five-atom ligand face, thus completing a closo 12 vertex polyhedron. In contrast, in the formally related species 10,11-μ-H-9-SMe2-7,8-nido-C2B9H10 and 10,11 -μ-(PPh3Au)-9-SMe2-7,8-nido-C2B9H10 the hydrogen atom and {Ph3PAu} fragment occupy bridging positions on an open face, whereas in anionic non-SMe2-substituted analogues of the last two the hydrogen atom and {Ph3PAu} fragment adopt endo-terminal sites. These differences in respect to the SMe2- substituted compounds are traced to the form of the HOMO of the [9-SMe2-7,8-nido- C2B9H10]t- ligand. Inspection of the three occupied π-MOs of this ligand additionally yields a semi-quantitative understanding of patterns visible in the facial BB, BC and CC distances of 3-PPh3-4-SMe2-3,1,2-closo-CuC2B9H10 10,11-μ-H-9-SMe2-7,8-nido-C2B9H10 and 10, 11-μ-(PPh3Au)-9-SMe2-7,8-nido-C2B9H10.

Original languageEnglish
Pages (from-to)471-476
Number of pages6
JournalPolyhedron
Volume10
Issue number4-5
DOIs
Publication statusPublished - 1991

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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