Scandium Arene Inverted-Sandwich Complexes Supported by a Ferrocene Diamide Ligand

作者：Huang Wenliang; Khan Saeed I; Diaconescu Paula L^*

来源：Journal of the American Chemical Society, 2011, 133(27): 10410-10413.

DOI：10.1021/ja204304f

The synthesis and characterization of the first scandium arene inverted-sandwich complexes supported by a ferrocene diamide ligand (NN(fc)) are reported. Through the use of (NN(fc))ScI(THF)(2) as a precursor and potassium graphite (KC(8)) as a reducing agent, the naphthalene and anthracene complexes [(NN(fc))Sc](2)(mu-C(10)H(8)) and [(NN(fc))Sc](2)(mu-C(14)H(10)), 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 [(NN(fc))Sc](2)(mu-C(14)H(10)) indicated that two different structures are accessible in solution. Reactivity studies showed that the naphthalene complex [(NN(fc))Sc](2)(mu-C(10)H(8)) can be converted to the corresponding anthracene species [(NN(fc))Sc](2)(mu-C(14)H(10)) and that [(NN(fc))Sc](2)(mu-C(10)H(8)) can act as either a reductant or a proton acceptor. The reaction of [(NN(fc))Sc](2)(mu-C(10)H(8)) with excess pyridine led to a rare example of C-C bond formation between two pyridine rings at the para position.

• 出版日期2011-7-13