Abstract
The electronic interactions between metals and dithiolenes are important in the biological processes of many metalloenzymes as well as in diverse chemical and material applications. Of special note is the ability of the dithiolene ligand to support metal centers in multiple coordination environments and oxidation states. To better understand the nature of metal-dithiolene electronic interactions, new capabilities in gas-phase core photoelectron spectroscopy for molecules with high sublimation temperatures have been developed and applied to a series of molecules of the type Cp 2M(bdt) (Cp = η 5-cyclopentadienyl, M = Ti, V, Mo, and bdt = benzenedithiolato). Comparison of the gas-phase core and valence ionization energy shifts provides a unique quantitative energy measure of valence orbital overlap interactions between the metal and the sulfur orbitals that is separated from the effects of charge redistribution. The results explain the large amount of sulfur character in the redox-active orbitals and the 'leveling' of oxidation state energies in metal-dithiolene systems. The experimentally determined orbital interaction energies reveal a previously unidentified overlap interaction of the predominantly sulfur HOMO of the bdt ligand with filled π orbitals of the Cp ligands, suggesting that direct dithiolene interactions with other ligands bound to the metal could be significant for other metal-dithiolene systems in chemistry and biology.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 11021-11031 |
| Number of pages | 11 |
| Journal | Inorganic Chemistry |
| Volume | 50 |
| Issue number | 21 |
| DOIs | |
| State | Published - Nov 7 2011 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry
Cite this
Metal-sulfur valence orbital interaction energies in metal-dithiolene complexes : Determination of charge and overlap interaction energies by comparison of core and valence ionization energy shifts. / Wiebelhaus, Nicholas J.; Cranswick, Matthew A.; Klein, Eric L.; Lockett, L. Tori; Lichtenberger, Dennis L; Enemark, John H.
In: Inorganic Chemistry, Vol. 50, No. 21, 07.11.2011, p. 11021-11031.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Metal-sulfur valence orbital interaction energies in metal-dithiolene complexes
T2 - Determination of charge and overlap interaction energies by comparison of core and valence ionization energy shifts
AU - Wiebelhaus, Nicholas J.
AU - Cranswick, Matthew A.
AU - Klein, Eric L.
AU - Lockett, L. Tori
AU - Lichtenberger, Dennis L
AU - Enemark, John H.
PY - 2011/11/7
Y1 - 2011/11/7
N2 - The electronic interactions between metals and dithiolenes are important in the biological processes of many metalloenzymes as well as in diverse chemical and material applications. Of special note is the ability of the dithiolene ligand to support metal centers in multiple coordination environments and oxidation states. To better understand the nature of metal-dithiolene electronic interactions, new capabilities in gas-phase core photoelectron spectroscopy for molecules with high sublimation temperatures have been developed and applied to a series of molecules of the type Cp 2M(bdt) (Cp = η 5-cyclopentadienyl, M = Ti, V, Mo, and bdt = benzenedithiolato). Comparison of the gas-phase core and valence ionization energy shifts provides a unique quantitative energy measure of valence orbital overlap interactions between the metal and the sulfur orbitals that is separated from the effects of charge redistribution. The results explain the large amount of sulfur character in the redox-active orbitals and the 'leveling' of oxidation state energies in metal-dithiolene systems. The experimentally determined orbital interaction energies reveal a previously unidentified overlap interaction of the predominantly sulfur HOMO of the bdt ligand with filled π orbitals of the Cp ligands, suggesting that direct dithiolene interactions with other ligands bound to the metal could be significant for other metal-dithiolene systems in chemistry and biology.
AB - The electronic interactions between metals and dithiolenes are important in the biological processes of many metalloenzymes as well as in diverse chemical and material applications. Of special note is the ability of the dithiolene ligand to support metal centers in multiple coordination environments and oxidation states. To better understand the nature of metal-dithiolene electronic interactions, new capabilities in gas-phase core photoelectron spectroscopy for molecules with high sublimation temperatures have been developed and applied to a series of molecules of the type Cp 2M(bdt) (Cp = η 5-cyclopentadienyl, M = Ti, V, Mo, and bdt = benzenedithiolato). Comparison of the gas-phase core and valence ionization energy shifts provides a unique quantitative energy measure of valence orbital overlap interactions between the metal and the sulfur orbitals that is separated from the effects of charge redistribution. The results explain the large amount of sulfur character in the redox-active orbitals and the 'leveling' of oxidation state energies in metal-dithiolene systems. The experimentally determined orbital interaction energies reveal a previously unidentified overlap interaction of the predominantly sulfur HOMO of the bdt ligand with filled π orbitals of the Cp ligands, suggesting that direct dithiolene interactions with other ligands bound to the metal could be significant for other metal-dithiolene systems in chemistry and biology.
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UR - http://www.scopus.com/inward/citedby.url?scp=80155142530&partnerID=8YFLogxK
U2 - 10.1021/ic201566n
DO - 10.1021/ic201566n
M3 - Article
C2 - 21988484
AN - SCOPUS:80155142530
VL - 50
SP - 11021
EP - 11031
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 21
ER -