Photoelectron spectroscopy and DFT calculations of easily ionized quadruply bonded Mo24+ compounds and their bicyclic guanidinate precursors

F. Albert Cotton, Jason C. Durivage, Nadine E. Gruhn, Dennis L. Lichtenberger, Carlos A. Murillo, Laura O. Van Dorn, Chad C. Wilkinson

Research output: Contribution to journalArticlepeer-review

24 Scopus citations


A series of five bicyclic guanidinate compounds containing various combinations of five- and six-membered rings and substituted alkyl groups have been shown by photoelectron spectroscopy to be easily ionized, with the one having two six-membered rings and four ethyl groups being the most easily ionized. The corresponding anions are capable of forming paddlewheel compounds having quadruply bonded Mo24+ units which are also easy to ionize. The most easily ionized compound is the ethyl-substituted Mo 2(TEhpp)4 complex which has a broad first ionization band centered around 4.27 ± 0.03 eV and an ionization onset at the very low energy of 3.93 ± 0.03 eV. Even the compound with ligands containing two five-membered rings, which favors a long Mo-Mo separation because of the large ligand bite, has an ionization energy (4.78 eV) that is less than those of well-known organometallic reducing agents such as (η5-C 9Me7)2Co and (η5-C 5Me5)2Cr.

Original languageEnglish (US)
Pages (from-to)19793-19798
Number of pages6
JournalJournal of Physical Chemistry B
Issue number40
StatePublished - Oct 12 2006

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry


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