Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 133, Issue 27, Pages 10410-10413Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja204304f
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- UCLA
- Sloan Foundation
- NSF
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0847735] Funding Source: National Science Foundation
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The synthesis and characterization of the first scandium arene inverted-sandwich complexes supported by a ferrocene diamide ligand (NNfc) are reported. Through the use of (NNfc)ScI(THF)(2) as a precursor and potassium graphite (KC8) as a reducing agent, the naphthalene and anthracene complexes [(NNfc)Sc](2)(mu-C10H8) and [(NNfc)Sc](2)(mu-C14H10), respectively, were synthesized and isolated in moderate to high yields. Both molecular structures feature an inverted-sandwich geometry and exhibit short Fe-Sc distances. DFT calculations were employed to gain understanding of the electronic structures of these new scandium arene complexes. A variable-temperature NMR spectroscopic study of [(NNfc)Sc](2)(mu-C14H10) indicated that two different structures are accessible in solution. Reactivity studies showed that the naphthalene complex [(NNfc)Sc](2)(mu-C10H8) can be converted to the corresponding anthracene species [(NNfc)Sc](2)(mu-C14H10) and that [(NNfc)Sc](2)(mu-C10H8) can act as either a reductant or a proton acceptor. The reaction of [(NNfc)Sc](2)(mu-C10H8) with excess pyridine led to a rare example of C-C bond formation between two pyridine rings at the para position.
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