Synthesis, Structural Analysis, and Functional Group Interconversion in the [closo-B10H8-1,10-X2]2 (X = CN, [OCRNMe2]+, OCOR, and [OH2]+) Derivatives

Litwin Jacob, Edyta Rzeszotarska, Anna Pietrzak, Victor G. Young, Piotr Kaszyński

Research output: Contribution to journalArticle

Abstract

Derivatives [closo-B10H8-1,10-(CN)2]2– and [closo-B10H8-1,10-(OCHNMe2)2], efficiently obtained from [closo-B10H8-1,10-(IPh)2] by nucleophilic substitution with CN and DMF, were envisioned as precursors to diacid [closo-B10H8-1,10-(COOH)2]2– and to dihydroxy derivative [closo-B10H8-1,10-(OH)2]2–, respectively. Attempts at hydrolysis or reduction of the dinitrile gave no reaction or complex mixtures of products. In contrast, the DMF adduct was cleanly hydrolyzed to diformate [closo-B10H8-1,10-(OCHO)2]2– and subsequently to protonated dihydroxy [closo-B10H8-1,10-(OH2)2]. The latter was O-acylated with PhCOCl. Crystal and molecular structures of five derivatives were established by single crystal XRD methods and compared to those for other [closo-B10H8-1,10-X2]2– derivatives. Trends in molecular geometry in the series and also reactivity of the dinitrile and intermediates were corroborated and correlated with DFT results (B3LYP/TZVP) by analysis of bonding, charge distribution and vibrational frequencies.

Original languageEnglish (US)
Pages (from-to)3083-3093
Number of pages11
JournalEuropean Journal of Inorganic Chemistry
Volume2020
Issue number32
DOIs
StatePublished - Aug 31 2020

Keywords

  • Boron
  • Cluster compounds
  • Density functional calculations
  • Structure elucidation
  • Synthesis design

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