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.

中文翻译：

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[closo-B10H8-1,10-X2] 2–（X = CN，[OCRNMe2] +，OCOR和[OH2] +）衍生物的合成，结构分析和官能团互换

衍生物[ closo- B ₁₀ H ₈ -1,10-（CN）₂ ] ^2–和[ closo- B ₁₀ H ₈ -1,10-（OCHNMe ₂）₂ ]是从[ closo- B ₁₀ H ₈通过CN ^–和DMF的亲核取代获得的‐1,10‐（IPh）₂ ]被设想为二酸[ closo- B ₁₀ H ₈ ‐1,10‐（COOH）₂ ] ^2-和二羟基衍生物[ closo的前体。 ‐B ₁₀H ₈ -1,10-（OH）₂ ] ^2–。水解或还原二腈的尝试未产生反应或产物的复杂混合物。与此相反，DMF加合物干净地水解为二甲酸酯[闭合碳-B ₁₀ ħ ₈ -1,10-（OCHO）₂ ] ^2-，随后质子化的二羟基[闭合碳-B ₁₀ ħ ₈ -1,10-（OH ₂）₂ ]。后者用PhCOCl进行O酰化。通过单晶XRD方法建立了五种衍生物的晶体和分子结构，并与其他[ closo- B₁₀ H ₈ -1,10-X ₂ ] ^2–导数。通过分析键合，电荷分布和振动频率，证实了该系列中分子几何学趋势以及​​二腈和中间体的反应性，并将其与DFT结果（B3LYP / TZVP）相关。