Photoelectron spectroscopy and DFT calculations of easily ionized quadruply bonded Mo2(4+) compounds and their bicyclic guanidinate precursors

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 ioni...

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Bibliographic Details
Published in:The journal of physical chemistry. B 2006-10, Vol.110 (40), p.19793-19798
Main Authors: Cotton, F Albert, Durivage, Jason C, Gruhn, Nadine E, Lichtenberger, Dennis L, Murillo, Carlos A, Van Dorn, Laura O, Wilkinson, Chad C
Format: Article
Language:English
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Summary: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 Mo2(4+) units which are also easy to ionize. The most easily ionized compound is the ethyl-substituted Mo2(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 (eta5-C9Me7)2Co and (eta5-C5Me5)2Cr.
ISSN:1520-6106
DOI:10.1021/jp061820m