Ligand Structural Effects on Cu<subscript>2</subscript>S<subscript>2</subscript> Bonding and Reactivity in Side-On Disulfido-Bridged Dicopper Complexes.
In: Inorganic Chemistry, Jg. 46 (2007-01-22), Heft 2, S. 486-496
academicJournal
Zugriff:
To assess supporting ligand effects on S-S bond activation, a series of [Cu2(μ-η²:η²-S2)]2+ complexes supported by various ,8-diketiminate or anilido-imine ligands (L) were synthesized via the reaction of Cu(I) precursors LCu-(CH3CN) with S8. For the cases where L = β-diketiminate, the syntheses were complicated by formation of clusters [Cu(SR)]4, where SR represents the ligand functionalized by sulfur at the central methine position. The [Cu2(μ-η²:η²-S2)]2+ products were characterized by X-ray crystallography and electronic absorption and resonance Raman spectroscopy. Correlations among the Cu-S, Cu-Cu, and S-S distances and the ν(S-S) values were observed and interpreted within the framework of a previously described bonding picture (Chen, P.; Fujisawa, K.; Helton, M. E.; Karlin, K. D.; Solomon, E. I. J. Am. Chem. Soc. 2003, 125, 6394). Comparison of these data to those for other relevant species revealed a remarkable degree of S-S bond activation in the compounds supported by the β-diketiminate and anilido-imine ligands, which through strong electron donation increase backbonding from the copper ions into the S-S σ orbital and cause S-S bond weakening. Reactions of one of the complexes supported by an anilido-imine ligand with PPha and xylyl isocyanide were explored, revealing facile transfer of sulfur to PPh3 but only displacement of sulfur to yield a LCu(I)-CNAr (Ar = xylyl) complex with the isocyanide. [ABSTRACT FROM AUTHOR]
Titel: |
Ligand Structural Effects on Cu<subscript>2</subscript>S<subscript>2</subscript> Bonding and Reactivity in Side-On Disulfido-Bridged Dicopper Complexes.
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Autor/in / Beteiligte Person: | Brown, Eric C. ; Bar-Nahum, Itsik ; York, John T. ; Aboelella, Nermeen W. ; Tolman, William B. |
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Zeitschrift: | Inorganic Chemistry, Jg. 46 (2007-01-22), Heft 2, S. 486-496 |
Veröffentlichung: | 2007 |
Medientyp: | academicJournal |
ISSN: | 0020-1669 (print) |
DOI: | 10.1021/ic061589r |
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