Exploration of bis(Nickelation) of 1,1-bis(o-carborane)

Dipendu Mandal, Georgina M. Rosair

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Abstract

The metalation of [Tl]2 [1-(1-3,1,2-closo-TlC2B9H10)-3,1,2-closo-TlC2B9H10 ], with the smaller {Ni(dmpe)} fragment sourced from [Ni(dmpe)Cl2 ], is explored. The bis(metalated) products are obtained as a diastereoisomeric mixture. These isomers were separated, fully characterised spec-troscopically and crystallographically and identified as rac-[1-(1-3-(dmpe)-3,1,2-closo-NiC2B9H10)-3-(dmpe)-3,1,2-closo-NiC2B9H10 ] (1) and meso-[1-(1-3-(dmpe)-3,1,2-closo-NiC2B9H10)-3-(dmpe)-3,1,2-closo-NiC2B9H10 ] (2). Previously, these 3,1,2-NiC2B9-3,1,2-NiC2B9 architectures (where both cages are not isomerised), were inaccessible, and thus new structures can be achieved during bis(nickelation) with {Ni(dmpe)}. Further, the metalation of the tetra-thallium salt with the bulky {Ni(dppe)} fragment sourced from [Ni(dppe)Cl2 ] was also studied. These bis(nickelated) products were also fully characterised and are afforded as the stereospecific species rac-[1-(1-3-(dppe)-3,1,2-closo-NiC2B9H10)-3-(dppe)-3,1,2-closo-NiC2B9H10 ] (3) and [1-(2-4-(dppe)-4,1,2-closo-NiC2B9H10)-3-(dppe)-3,1,2-closo-NiC2B9H10 ] (4α). In the latter metalation, compound 3 shows intramolecular dihydrogen bonding, contributing to the stereospecificity, whereas isomerisation from 3,1,2 to 4,1,2-in the 4α is related to steric relief.

Original languageEnglish
Article number16
JournalCrystals
Volume11
Issue number1
Early online date27 Dec 2020
DOIs
Publication statusPublished - Jan 2021

Keywords

  • 1,1-bis(o-carborane)
  • Bis(nickelation)
  • Deboronation
  • Diastereoisomers
  • Metalation
  • Stereospecific

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Inorganic Chemistry

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