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Synthesis, Structural Analysis, and Functional Group Interconversion in the [ closo ‐B 10 H 8 ‐1,10‐X 2 ] 2 – (X = CN, [OCRNMe 2 ] + , OCOR, and [OH 2 ] + ) Derivatives
Author(s) -
Jacob Litwin,
Rzeszotarska Edyta,
Pietrzak Anna,
Young Victor G.,
Kaszyński Piotr
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000456
Subject(s) - chemistry , reactivity (psychology) , protonation , adduct , crystal structure , crystallography , hydrolysis , nucleophile , nucleophilic substitution , borane , bond length , stereochemistry , derivative (finance) , hydrogen bond , molecule , medicinal chemistry , organic chemistry , catalysis , medicine , ion , alternative medicine , pathology , financial economics , economics
Derivatives [ closo ‐B 10 H 8 ‐1,10‐(CN) 2 ] 2– and [ closo ‐B 10 H 8 ‐1,10‐(OCHNMe 2 ) 2 ], efficiently obtained from [ closo ‐B 10 H 8 ‐1,10‐(IPh) 2 ] by nucleophilic substitution with CN – and DMF, were envisioned as precursors to diacid [ closo ‐B 10 H 8 ‐1,10‐(COOH) 2 ] 2– and to dihydroxy derivative [ closo ‐B 10 H 8 ‐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 ‐B 10 H 8 ‐1,10‐(OCHO) 2 ] 2– and subsequently to protonated dihydroxy [ closo ‐B 10 H 8 ‐1,10‐(OH 2 ) 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 ‐B 10 H 8 ‐1,10‐X 2 ] 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.