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Electronic Structures of Reduced and Superreduced Ir_2(1,8-diisocyanomenthane)_4^(n+) Complexes

Záliš, Stanislav and Hunter, Bryan M. and Gray, Harry B. and Vlček, Antonín (2017) Electronic Structures of Reduced and Superreduced Ir_2(1,8-diisocyanomenthane)_4^(n+) Complexes. Inorganic Chemistry, 56 (5). pp. 2874-2883. ISSN 0020-1669.

[img] PDF (Calculated IR and UV–vis spectra of the 3:1 orientational isomer of 2+, 1+, and 0; frontier MO compositions of both deformational isomers of 2+, 1+, and 0; figures showing 1+ spin density distribution and spectroscopically important MOs of 2+, 1+, and 0) - Supplemental Material
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Molecular and electronic structures of Ir_2(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 [Pt_2(μ-P_2O_5(BF_2)_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.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Hunter, Bryan M.0000-0001-8559-9304
Gray, Harry B.0000-0002-7937-7876
Alternate Title:Electronic Structures of Reduced and Superreduced Ir2(1,8-diisocyanomenthane)4n+ Complexes
Additional Information:© 2017 American Chemical Society. Received: December 8, 2016; Published: February 20, 2017. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124). Additional support was provided by the Arnold and Mabel Beckman Foundation, the Ministry of Education of the Czech Republic (grant LD14129), and COST Actions CM1202 and CM1405.
Group:CCI Solar Fuels
Funding AgencyGrant Number
Arnold and Mabel Beckman FoundationUNSPECIFIED
Ministry of Education (Czech Republic)LD14129
COST ActionCM1202
COST ActionCM1405
Issue or Number:5
Record Number:CaltechAUTHORS:20170221-141613246
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Official Citation:Electronic Structures of Reduced and Superreduced Ir2(1,8-diisocyanomenthane)4n+ Complexes Stanislav Záliš, Bryan M. Hunter, Harry B. Gray, and Antonín Vlček Inorganic Chemistry 2017 56 (5), 2874-2883 DOI: 10.1021/acs.inorgchem.6b03001
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:74435
Deposited By: Tony Diaz
Deposited On:21 Feb 2017 22:31
Last Modified:09 Mar 2020 13:19

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