Structure, magnetic properties and epoxidation activity of iron(III) salicylaldimine complexes
Resource
Journal of the Chemical Society, Dalton Transactions 2000: 915-918
Journal
Journal of the Chemical Society Dalton Transactions
Pages
915-918
Date Issued
2000
Date
2000
Author(s)
Shyu, Huey-Lih
Wei, Ho-Hsiang
Lee, Gene-Hsaing
Wang, Yu
Abstract
Two new iron(III) complexes with salicylaldimine ligands, [Fe(L1)Cl]·CH3CN (1) and [Fe(L2)Cl(H2O)]·1/3CH3Cl (2) [H2L1 = N,N′-(1,1-dimethylethylene)bis(salicylaldimine), H2L2 = N,N′-(1,1-dimethylethylene)bis(3-methoxysalicylaldimine)], have been prepared and characterized. The X-ray crystal structure analysis shows that the iron(III) ion in complex 1 is in a distorted square pyramidal environment, while in 2, the iron(III) center is six-coordinate with distorted octahedral geometry. The Schiff base ligands L1 and L2 occupied the basal sites, with chloride and water occupying the apical sites. Magnetic susceptibility and Mössbauer effect measurements showed a high-spin configuration (S = 5/2) for Fe(III) in 1 and 2. The temperature dependence of the magnetic data for complexes 1 and 2 is analyzed in terms of the spin-Hamiltonian formalism, which gives an accurate estimate of the zero-field splitting of the ground state of the iron(III) ions as D = 10.2 cm−1 (E = 3.4 cm−1) and D = 7.2 cm−1 (E = 2.4 cm−1, zJ′ = −0.5 cm−1), respectively, in the above two complexes. It has been found for the first time that complexes 1 and 2 activate the epoxidation of cis-stilbene by NaOCl. With 1, the epoxides were produced in 40% yield with cis∶trans = 20∶80, and with 2, the epoxides were produced in 90% yield with cis∶trans = 40∶60.
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