SYNTHESIS, CHARACTERIZATION, AND REACTIVITY OF NEW HETEROLEPTIC HETEROBIMETALLIC ALKOXIDE DERIVATIVES OF TIN(II) - X-RAY CRYSTAL-STRUCTURESOF [CLSN(M(2)(OPRI)(9))](2) (M=ZR, HF), [(C5H5)SN(ZR-2(OPRI)(9))], AND [(C5H5)PB(MU(2)-OBU(T))(2)SN(OBU(T))]

The synthesis of new cyclopentadienyl-containing heterobimetallic alko xides has been accomplished by employing the alkoxide precursors towar d cyclopentadienyl reagents (NaCp and (C5H5)SnCl). The equimolar react ions of anhydrous SnX(2) (X = Cl, I) and KM(2)(OPri)(9) (M = Zr, Hf) o ffer halide heterobimetallic isopropoxides [XSn{M(2)(OPri)(9)}](2) (1, M = Hf, X = Cl; 2, M = Hf, X = I; 3, M = Zr, X = Cl) in quantitative yields. Both 1 and 3 react with NaCp in benzene-THF to give (C5H5)Sn{M (2)(OPri)(9)} (4, M = Hf; 5, M = Zr). Alternatively, 4 and 5 are conve niently obtained by the equimolar reaction of (C5H5)SnCl with KM(2)(OP ri)(9) (M = Zr, Hf). Although the reaction (1:1) of (C5H5)SnCl with [K Ge(OBu(t))(3)](n) affords the expected product (C5H5)Sn(mu(2)-OBu(t))( 2)Ge(OBu(t)) (6), the reaction with [KPb(OBu(t))(3)](n) shows a transf er of cyclopentadienyl ring from tin to lead to provide (C5H5)Pb(mu(2) -OBu(t))(2)Sn(OBu(t)) (7). The new derivatives have been readily chara cterized by elemental analysis, multinuclear (H-1, C-13, Sn-119, and P b-207) NMR studies, molecular weight measurements, and volatility. A s ingle-crystal X-ray diffraction study is reported for the compounds 1, 3, and 5-7. The solid state structures of 1, 3, and 5 exhibit varying coordination behavior of M(2)(OPri)(9)(-) units to SnX(+) (X = C5H5, Cl) fragments. In the structural framework of the tert-butoxide deriva tives, the four membered MM'(mu(2)-OBu(t))(2) (6, M = Ge, M' = Sn; 7, M = Pb, M' = Sn) ring is terminated at the metal ends by cyclopentadie nyl and tert-butoxide ligands and each of the metals, bearing a stereo chemically active lone pair, displays a pyramidal geometry.