Electronic Structures of Reduced and Superreduced Ir2(1,8-diisocyanomenthane)4n+ Complexes

Stanislav Záliš*, Bryan M. Hunter, Harry B. Gray, Antonín Vlček

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

4 Scopus citations


Molecular and electronic structures of Ir2(1,8-diisocyanomenthane)4n+ (Ir(dimen)n+) complexes have been investigated by DFT for n = 2, 1, 0 (abbreviated 2+, 1+, 0). Calculations reproduced the experimental structure of 2+, ν(CN) IR, and visible absorption spectra of all three oxidation states, as well as the EPR spectrum of 1+. We have shown that the two reduction steps correspond to successive filling of the Ir-Ir pσ orbital. Complexes 2+ and 1+ have very similar structures with 1+ having a shorter Ir-Ir distance. The unpaired electron density in 1+ is delocalized along the Ir-Ir axis and over N atoms of the eight CN- ligands. The second reduction step 1+ → 0 changes the Ir(CN−)4 coordination geometry at each Ir site from approximately planar to seesaw whereby one −NC-Ir-CN- moiety is linear and the other bent at the Ir (137°) as well as N (146°) atoms. Although complex 0 is another example of a rare (pσ)2 dimetallic species (after [Pt2(μ-P2O5(BF2)2)4]6-, J. Am. Chem. Soc. 2016, 138, 5699), the redistribution of lower lying occupied molecular orbitals increases electron density predominantly at the bent CN- ligands whose N atoms are predicted to be nucleophilic reaction centers.

Original languageEnglish (US)
Pages (from-to)2874-2883
Number of pages10
JournalInorganic chemistry
Issue number5
StatePublished - Mar 6 2017

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry


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