Understanding the behavior of halogens as hydrogen bond acceptors
Understanding the behavior of halogens as hydrogen bond acceptors
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DOI：
10.1021/cg0l5522k
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发表时间：
2001-07-01
影响因子：
3.8
通讯作者：
Sherwood, P
中科院分区：
文献类型：
--
作者：
Brammer, L;Bruton, EA;Sherwood, P
碳结合和末端金属结合的卤素和卤素离子作为潜在的氢键受体的行为之间的相似性和差异已经通过检查晶体结构中存在的数千种相互作用进行了广泛的研究。卤素在这些环境中的每一个被发现从事氢键，这些相互作用的几何偏好已经建立。典型的H…X = F时的X-M角与X = Cl、Br、I时的X-M角明显不同。此外，中等强氢键受体X-M和弱得多的受体X-C的行为之间存在显著的相似性。所观察到的几何偏好的根本原因已经建立了从头计算的分子轨道计算使用合适的模型系统。结果的背景下，其潜在的应用在晶体工程和超分子化学，包括相关的成核卤化溶剂。更广泛的影响，如卤代烃配位化学，二元金属卤化物固态化学，弱配位阴离子的研究领域的结果进行了讨论。
The similarities and differences between the behavior of carbon-bound and terminal metal-bound halogens and halide ions as potential hydrogen bond acceptors has been extensively investigated through examination of many thousands of interactions present in crystal structures. Halogens in each of these environments are found to 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 significant parallels between the behavior of moderately strong hydrogen bond acceptors X-M and the much weaker acceptors X-C. The underlying reasons for the observed geometric preferences have been established by ab initio molecular orbital calculations using suitable model systems. The results are presented within the context of their potential applications in crystal engineering and supramolecular chemistry, including relevance to nucleation in halogenated solvents. The broader implications of the results in areas such as halocarbon coordination chemistry, binary metal halide solid-state chemistry, and the study of weakly coordinating anions are also discussed.