Electrophilicity of aliphatic nitrilium closo-decaborate clusters: Hyperconjugation provides an unexpected inverse reactivity order

Valeria K. Burianova, Alexander S. Mikherdov, Dmitrii S. Bolotin, Alexander S. Novikov, Pennie Petrus Mokolokolo, Andreas Roodt, Vadim P. Boyarskiy, Vitalii V. Suslonov, Andrey P. Zhdanov, Konstantin Yu Zhizhin, Nikolay T. Kuznetsov

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

The nucleophilic addition of 2-pyridyl carbamidoxime to the C≡N group of the aliphatic nitrilium closo-decaborate clusters (PhCH2PPh3)[B10H9NCR] (R = Me, Et, and iPr) proceeds to give 2-iminium closo-decaborates (68–88% isolated yields). A systematic kinetic and theoretical study of the nucleophilic addition indicates that the reactivity of the nitrile ligand at the boron cluster unexpectedly increases in the order of R: Me < Et < iPr. It was shown theoretically, that the electrophilicity of the C≡N group is primarily determined by hyperconjugation with the neighboring aliphatic moiety, which induced by substantial (ca. +0.6 e) positive charge at the nitrile C atom.

Original languageEnglish
Pages (from-to)97-103
Number of pages7
JournalJournal of Organometallic Chemistry
Volume870
Issue number870
DOIs
StatePublished - 1 Sep 2018

Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Keywords

  • Amidoxime
  • Hyperconjugation
  • Nitrilium salts
  • Nucleophilic addition
  • Oxime

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