Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex

Research output: Contribution to journalArticle

  • External authors:
  • Benedict M Gardner
  • Gabor Balazs
  • Manfred Scheer
  • Ashley J Wooles
  • Jonathan McMaster
  • William Lewis
  • Alexander J Blake

Abstract

he HAsAsH molecule has hitherto only been proposed tentatively as a short-lived species generated in electrochemical or microwave-plasma experiments. After two centuries of inconclusive or disproven claims of HAsAsH formation in the condensed phase, we report the isolation and structural authentication of HAsAsH in the diuranium(IV) complex [{U(TrenTIPS)}2(μ-η2:η2-As2H2)] (3, TrenTIPS=N(CH2CH2NSiPri 3)3; Pri=CH(CH3)2). Complex 3 was prepared by deprotonation and oxidative homocoupling of an arsenide precursor. Characterization and computational data are consistent with back-bonding-type interactions from uranium to the HAsAsH π∗-orbital. This experimentally confirms the theoretically predicted excellent π-acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane-1,2-diide form

Bibliographical metadata

Original languageEnglish
Pages (from-to)15250-15254
Number of pages4
JournalAngewandte Chemie (International Edition)
Volume54
DOIs
StatePublished - 28 Oct 2015