Understanding the Behavior of Halogens as Hydrogen Bond Acceptors

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• 作者：Lee Brammer ; Eric A. Bruton ; and Paul Sherwood
• 刊名：Crystal Growth & Design
• 出版年：2001
• 出版时间：July 2001
• 年：2001
• 卷：1
• 期：4
• 页码：277 - 290
• 全文大小：672K
• 年卷期：v.1,no.4(July 2001)
• ISSN：1528-7505

文摘

The similarities and differences between the behavior of carbon-bound and terminal metal-boundhalogens and halide ions as potential hydrogen bond acceptors has been extensively investigated through examinationof many thousands of interactions present in crystal structures. Halogens in each of these environments are foundto engage in hydrogen bonding, and geometric preferences for these interactions have been established. Notably,typical H···X-M angles are markedly different for X = F than for X = Cl, Br, I. Furthermore, there are significantparallels between the behavior of moderately strong hydrogen bond acceptors X-M and the much weaker acceptorsX-C. The underlying reasons for the observed geometric preferences have been established by ab initio molecularorbital calculations using suitable model systems. The results are presented within the context of their potentialapplications in crystal engineering and supramolecular chemistry, including relevance to nucleation in halogenatedsolvents. The broader implications of the results in areas such as halocarbon coordination chemistry, binary metalhalide solid-state chemistry, and the study of weakly coordinating anions are also discussed.