W2(O-t-Bu)6 reacts with binaphthol derivatives (H2BINO, R = H (1); H2Me2BINO, R = CH3 (2)) to produce monosubstituted products of the formula (R2BINO) W2(O-t-Bu)4. The presence of a single product in the 1H NMR spectra of these compounds supports the hypothesis that the binaphtholate ligand adopts a preferential mode of binding. Disubstituted products can be formed when 2 equiv of binaphthol is reacted with W2(O-t-Bu)6: racemic binaphthol generates anti-(R,S)-(BINO)2W2(O-t-Bu)2 (3) with small quantities of anfi-(R*,R*)-(BINO)2W2(O-t-Bu)2 (5), while optically pure (R)-binaphthol yields gauche-(R,R)-(BINO)2W2(O-t-Bu)2 (6). The enantiomers of 6 appear to undergo intermolecular exchange reactions in the presence of tert-butyl alcohol, forming 3 as the main product along with small quantities of (R*,R*,R*)-(BINO)3W2 (4). A reaction between 2 and 2 equiv of acetylene generates a flyover complex, (μ2-C4H4)(Me2BINO)W2(O-t-Bu)4 (7), as identified by 1H and 13C NMR spectroscopy. When greater than 6 equiv of acetylene is employed, (η2-C2H2)(μ2-C4H4)(Me2BINO)2W2(O-t-Bu)2 (8), a complex containing a flyover fragment with an additional terminal acetylene ligand, is produced. Complex 3 is also reactive toward acetylene, generating diastereomeric tris(acetylene) derivatives of the formula (μ2-C4H4)-(η2-C2H2)(BINO)2W2(O-t-Bu)2 (9) in a nonstatistical ratio. This result suggests that the presence of chiral chelating ligands in the coordination sphere can influence the stereochemistry of complex formation at the W2 template.