Electronic Structures of Reduced and Superreduced Ir 2 (1,8-diisocyanomenthane) 4 n+ Complexes.

Molecular and electronic structures of Ir2 (1,8-diisocyanomenthane)4 n+ (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-P2 O5 (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.