Cationic Copper Hydride Clusters Arising from Oxidation of (Ph3P)6Cu6H6

Shuo Liu, Michael S. Eberhart, Jack R. Norton, Xiaodong Yin, Michelle C. Neary, Daniel W. Paley

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

Transfer of the first electron from (Ph3P)6Cu6H6 to Cp∗2Fe+ is fast (k > 106 L·mol-1·s-1). Transfer of a second electron to the same oxidant has a much lower thermodynamic driving force and is considerably slower, with k = 9.29(4) × 103 L·mol-1·s-1. The second oxidation leads to the formation of [(Ph3P)6Cu6H5]+. The structure of [(Ph3P)6Cu6H5]+ has been confirmed by its conversion back to (Ph3P)6Cu6H6 and by microanalysis; X-ray diffraction shows that the complex is a bitetrahedron in the solid state. [(Ph3P)6Cu6H5]+ can also be prepared by treating (Ph3P)6Cu6H6 with MeOTf. With less than 1 equiv of Cp∗2Fe+ as oxidant, (Ph3P)6Cu6H6 gives [(Ph3P)7Cu7H6]+ as the major product; X-ray diffraction shows a Cu6 octahedron with one face capped by an additional Cu. [(Ph3P)7Cu7H6]+ can also be prepared by treating (Ph3P)6Cu6H6 with [Cu(CH3CN)4]+ (along with 1 equiv of Ph3P), and can be converted back to (Ph3P)6Cu6H6 with base/H2.

Original languageEnglish (US)
Pages (from-to)7685-7688
Number of pages4
JournalJournal of the American Chemical Society
Volume139
Issue number23
DOIs
StatePublished - Jun 14 2017
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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