X-ray Absorption Spectroscopic and Computational Investigation of a Possible S⋯S Interaction in the [Cu<subscript>3</subscript>S<subscript>2</subscript>]<superscript>3+</superscript> Core.
In: Journal of the American Chemical Society, Jg. 133 (2011-11-02), Heft 43, S. 17180-17191
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Zugriff:
The electronic structure of the [Cu3S2]3+ core of [(LCu)3(S)2]3+ (L = N,N,N',N'-tetramethyl-2R,3R-cyclohexanediamine) is investigated using a combination of Cu and S K-edge X-ray absorption spectroscopy and calculations at the density functional and multireference second-order perturbation levels of theory. The results show that the [Cu3S2]3+ core is best described as having all copper centers close to but more oxidized than Cu2+, while the charge on the S2 fragment is between that of a sulfide (S2-) and a subsulfide (S23-) species. The [Cu3S2]3+ core thus is different from a previously described, analogous [Cu3O2]3+ core, which has a localized [(Cu3+Cu2+Cu2+)(O2-)2]3+ electronic structure. The difference in electronic structure between the two analogues is attributed to increased covalent overlap between the Cu 3d and S 3p orbitals and the increased radial distribution function of the S 3p orbital (relative to O 2p). These features result in donation of electron density from the S-S σ* to the Cu and result in some bonding interaction between the two S atoms at 2.69 Å in [Cu3S2]3+, stabilizing a delocalized S = 1 ground state. [ABSTRACT FROM AUTHOR]
Titel: |
X-ray Absorption Spectroscopic and Computational Investigation of a Possible S⋯S Interaction in the [Cu<subscript>3</subscript>S<subscript>2</subscript>]<superscript>3+</superscript> Core.
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Autor/in / Beteiligte Person: | Sarangi, Ritimukta ; Yang, Lei ; Winikoff, Stuart G. ; Gagliardi, Laura ; Cramer, Christopher J. ; Tolman, William B. ; Solomon, Edward I. |
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Zeitschrift: | Journal of the American Chemical Society, Jg. 133 (2011-11-02), Heft 43, S. 17180-17191 |
Veröffentlichung: | 2011 |
Medientyp: | academicJournal |
ISSN: | 0002-7863 (print) |
DOI: | 10.1021/ja111323m |
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