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 CP2MCl2 (M = Ti, Zr, Hf) as CpH in the presence of M'L-2 or M'L'(2) (M' = Ca, Sr, Mn; CH3OCH2CH2OH = LH or (CH3)(2)NCH2CH2OH = L'H) in an alcohol as a source of protons. In the reactions presented, a series of compounds, [Ca4Ti2(mu(6)-O)(mu(3,)eta(2)-L)(8)(eta-L)(2)Cl-4] (1), (Sr4Hf2(mu(6)-O)(mu(3),eta(2)-L)(8)(eta-L)(2)(eta-LH)(4)Cl-4] (2), [Ca4Zr2(mu(6)-O)(mu-Cl)(4)(mu,eta(2)- L)(8)Cl-2] (3), [Sr4Ti2(mu(6)-O)(mu(3),eta(2)-L)(8)(eta-L)(2)(eta-LH)(2)Cl-4] (4) [Ca4Zr2Cp2(mu(4)-Cl)(mu-Cl)(3)(mu(3),eta(2)-L)(4)(mu,eta(2)-L)(4)Cl-2] (5), [CaTiCl2(mu,eta(2)-L')(3)(eta-L'H)(3)[L'] (6), (Ca2Ti(mu,eta(2)-L')(6)Cl-2] (7), [Mn4Ti4(mu-Cl)(2)(mu(3)-eta(2)-L)(10)Cl-6] (8), and [Mn10Zr10(mu(4)-O)(10)(mu(3)-O)(4)(mu(3),eta(2)-L)(2)(mu,eta(2)-L)(16)(m u,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.