Synthesis of bimetallic complexes via 4-stannatetrahydro-s-indacenes

4-Stanna-8-silatetrahydro-4,4,8,8-tetramethyl-s-indacene (4) reacts with CpTiCI3 and CpZrCl3.2THF in toluene (ratio 1:1) to give monotransmetallated products CPMC12 (eta5-C5H4SiMe2C5H4SnMe2CI) (M = Ti (5), Zr (6)) in high yields. These compounds can be transformed into heteronuclear complexes of type L(n)MCp-SiMe2-CpM'L'm (ML, = TiCl2CP, M'L'm = Rh(COD), 10; ML(n) = ZrCl2CP, M'L'm = Rh(COD), 11; ML(n) = ZrCl2CP, M'L'm = TiCl2CP, 12; ML(n) = ZrCl2CP, M'L'm = ZrCl2CP*, 13) in reactions with [Rh(COD)Cl]2, CpTiCI3, and Cp*ZrCl3, respectively. Compound 4 and its heteroanalog 4-stannatetra-hydro-4,4,8,8-tetramethyl-s-indacene (14) react with CpTiCI3 (ratio 1:2) and (Cl3TiCP)2SiMe2 (16) (ratio 1:1) to give the corresponding monobridged [CpTiCl2(eta5-C5H4)]2XMe2 (X = C (15), Si (8)) and doubly-bridged (eta5:eta5-C5H4SiMe2C5H4) (eta5:eta5-C5H4XMe2C5H4)(TiCl2)2 (X = C (17), Si (18)) Ti(IV) derivatives. They may be reduced by powdered zinc in toluene to the corresponding Ti(III) complexes, [CpTiCl(eta5-C5H4)]2XMe2 (X = C (20), Si (21)) and (eta5:eta5-C5H4SiMe2C5H4) (eta5:eta5-C5H4XMe2C5H4)(TiCl)2 (X = C (22), Si (23)). Crystals of 23 are monoclinic, space group P2(1)/a with unit cell dimensions a = 16.033 (3) angstrom, b = 18.859 (4) angstrom, c = 7.997 (2) angstrom, gamma = 96.82 (2)-degrees, and Z = 4.