Revisiting Ir(CO)3Cl

Yuta Tsuji, Roald Hoffmann, Joel S. Miller

Research output: Contribution to journalArticlepeer-review

9 Citations (Scopus)


We return to an old puzzle - the short metal-metal separation and electrical conductivity of the apparently unoxidized one-dimensionally stacked structure of a d8 Ir(I) complex, Ir(CO)3Cl. One would expect neither a short Ir-Ir distance of 2.84 Å, nor metallicity in an unoxidized stacked square-planar d8 array. We build up dimer, trimer, one-dimensional polymer and model 3-dimensional structures, in both molecular and extended structure plane wave calculations. The short Ir-Ir separation in the polymer, with a substantial contribution of 6pz-5dz2 bonding to it, is obtained without any oxidation. There is computational evidence for an important level crossing in the polymer. The metallicity remains unexplained, but likely arises from partial oxidation. And that remains an outstanding experimental issue.

Original languageEnglish
Pages (from-to)141-149
Number of pages9
Publication statusPublished - Jan 8 2016
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


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