Derivatives [closo-B10H8-1,10-(CN)2]2– and [closo-B10H8-1,10-(OCHNMe2)2], efficiently obtained from [closo-B10H8-1,10-(IPh)2] by nucleophilic substitution with CN– and DMF, were envisioned as precursors to diacid [closo-B10H8-1,10-(COOH)2]2– and to dihydroxy derivative [closo-B10H8-1,10-(OH)2]2–, respectively. Attempts at hydrolysis or reduction of the dinitrile gave no reaction or complex mixtures of products. In contrast, the DMF adduct was cleanly hydrolyzed to diformate [closo-B10H8-1,10-(OCHO)2]2– and subsequently to protonated dihydroxy [closo-B10H8-1,10-(OH2)2]. The latter was O-acylated with PhCOCl. Crystal and molecular structures of five derivatives were established by single crystal XRD methods and compared to those for other [closo-B10H8-1,10-X2]2– derivatives. Trends in molecular geometry in the series and also reactivity of the dinitrile and intermediates were corroborated and correlated with DFT results (B3LYP/TZVP) by analysis of bonding, charge distribution and vibrational frequencies.
- Cluster compounds
- Density functional calculations
- Structure elucidation
- Synthesis design