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Sobota P, Drag-Jarzabek A, John L, Utko J, Jerzykiewicz LB, Duczmal M: Cyclopentadienyl/Alkoxo Ligand Exchange in Group 4 Metallocenes: A Convenient Route to Heterometallic Species. Inorg Chem. 2009 Jun 15.
A simple and efficient strategy for the synthesis of nonorganometallic heterometallic clusters from cheap organometallic precursors is reported. This unique synthetic method involves elimination of the cyclopentadienyl ring from Cp (2) MCl (2) (M = Ti, Zr, Hf) as CpH in the presence of M'L (2) or M'L'(2) (M' = Ca, Sr, Mn; CH (3) OCH (2) CH (2) OH = LH or (CH (3))(2) NCH (2) CH (2) OH = L'H) in an alcohol as a source of protons. In the reactions presented, a series of compounds, [Ca (4) Ti (2)(mu (6)-O)(mu (3),eta (2)-L)(8)(eta-L)(2) Cl (4)] (1), [Sr (4) Hf (2)(mu (6)-O)(mu (3),eta (2)-L)(8)(eta-L)(2)(eta-LH)(4) Cl (4)] (2), [Ca (4) Zr (2)(mu (6)-O)(mu-Cl)(4)(mu,eta (2)-L)(8) Cl (2)] (3), [Sr (4) Ti (2)(mu (6)-O)(mu (3),eta (2)-L)(8)(eta-L)(2)(eta-LH)(2) Cl (4)] (4), [Ca (4) Zr (2) Cp (2)(mu (4)-Cl)(mu-Cl)(3)(mu (3),eta (2)-L)(4)(mu,eta (2)-L)(4) Cl ( 2)] (5), [CaTiCl (2)(mu,eta (2)-L')(3)(eta-L'H)(3)][L'] (6), [Ca (2) Ti (mu,eta (2)-L')(6) Cl (2)] (7), [Mn (4) Ti (4)(mu-Cl)(2)(mu (3),eta (2)-L)(2)(mu,eta (2)-L)(10) Cl (6)] (8), and [Mn (10) Zr (10)(mu (4)-O)(10)(mu (3)-O)(4)(mu (3),eta (2)-L)(2)(mu,eta (2)-L)(16) (mu,eta-L)(4)(eta-L)(2) Cl (8)] (9), were obtained in good yield. All of the complexes were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray structural analysis. Complex 8 belongs to a group of magnetic clusters that consists of Mn (4) subunits held together by two mu-Cl bridges. Compounds 6 and 7 underwent thermal decomposition, yielding an alternative source for some heterometallic oxides, which were analyzed by X-ray powder diffraction. |
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