Synthesis, Structural Analysis, and Functional Group Interconversion in the [closo‐B10H8‐1, 10‐X2]2– (X = CN, [OCRNMe2]+, OCOR, and [OH2]+) Derivatives. Issue 32 (14th July 2020)

• Record Type: Journal Article
• Authors: Jacob, Litwin; Rzeszotarska, Edyta; Pietrzak, Anna; Young, Victor G.; Kaszyński, Piotr
• Is Part Of: European journal of inorganic chemistry. Issue 32(2020)
• Page Start: 3083
• Page End: 3093
• Publication Date: 2020-07-14
• Subjects: Boron -- Cluster compounds -- Synthesis design -- Structure elucidation -- Density functional calculations; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202000456
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Derivatives [ closo ‐B10 H8 ‐1, 10‐(CN)2 ] 2– and [ closo ‐B10 H8 ‐1, 10‐(OCHNMe2 )2 ], efficiently obtained from [ closo ‐B10 H8 ‐1, 10‐(IPh)2 ] by nucleophilic substitution with CN – and DMF, were envisioned as precursors to diacid [ closo ‐B10 H8 ‐1, 10‐(COOH)2 ] 2– and to dihydroxy derivative [ closo ‐B10 H8 ‐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 ‐B10 H8 ‐1, 10‐(OCHO)2 ] 2– and subsequently to protonated dihydroxy [ closo ‐B10 H8 ‐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 ‐B10 H8 ‐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. Abstract : Readily available [ closo ‐B10 H8 ‐1, 10‐(IPh)2 ] is a convenient precursor to 1, 10‐difunctional derivatives of the [ closo ‐B10 H10 ] 2 – anion through nucleophilic substitution and subsequent functional group interconversion, such as hydrolysis and esterification, which turned out to be surprising.