Reaction of optically pure (S,S)-butadiene diepoxide (1) with 2 equiv of Grignard reagent ArMgBr (Ar = 2-CF3C6H4 or 3,5-Me2C6H3) in the presence of copper(I) iodide produces the chiral substituted diphenylbutanediols (dpbd) (2S,3S)-ArCH2CH(OH)CH(OH)CH2Ar (Ar = 2-CF3C6H4 (2), abbreviated 2-CF3-dpbdH2; Ar = 3,5-Me2C6H3 (3), abbreviated 3,5-Me2-dpbdH2). The mono(pentamethylcyclopentadienyl) halide complex (η-C5Me5)TiCl3 reacts with 1 equiv of diol 2 in the presence of triethylamine to produce the dimeric species [(η-C5Me5)TiCl(μ-η1,η1-2-CF3-dpbd)]2 (4). An analogous reaction employing the zirconium halide (η-C5Me5)ZrCl3 and the diol 3 leads to isolation of the salt complex [HNEt3][(η-C5Me5)2Zr2Cl2(μ-Cl)(μ-η1,η2-3,5-Me2-dpbd)2] (5). Compounds 4 and 5 have been subjected to single-crystal X-ray diffraction studies. The solid-state structure of 4 consists of two titanium metal centers, each bearing a pentamethylcyclopentadienyl ligand and a terminal chloride ligand, bridged by two diolate ligands such that a central 10-membered ring is formed. The terminal Ti−Cl bond length is 2.306(2) Å, and the Ti−O distances range from 1.783(4) to 1.830(5) Å. The two bridging diolate ligands adopt widely differing conformations such that one diolate ligand possesses Ti−O−C angles of 172.3(4) and 172.4(4)° while the other displays acute Ti−O−C angles of 125.2(4)°. The molecular geometry of the anion in 5 is comprised of two (η-C5Me5)ZrCl moieties bridged by a single μ2-Cl ligand and two diolate ligands. One oxygen atom within each diolate ligand acts as a μ2 bridge between the zirconium metal centers whereas the other is bound in a terminal fashion to one metal center, thus forming a central Zr2O2 four-membered ring and two ZrO2C2 five-membered rings. Bridging Zr−Cl distances are 2.606(4) and 2.737(3) Å, and terminal Zr−Cl bond lengths are 2.499(4) and 2.584(4) Å. Terminal Zr−O distances are 1.989(9) and 1.972(9) Å, and bridging Zr−O distances range from 2.125(9) to 2.222(8) Å. Crystal data for 4 (at −90 °C): monoclinic space group P21, a = 12.399(1), b = 22.229(2), c = 13.275(1) Å, β = 111.208(6)°, V = 3411 Å3, Z = 2, Dcalc = 1.338 g cm-3. Crystal data for 5 (at −90 °C): orthorhombic space group P212121, a = 13.615(2), b = 13.623(2), c = 36.042(5) Å, V = 6685 Å3, Z = 4, Dcalc = 1.246 g cm-3.