Partially fluorinated alkanes, arenes, and alkenes can be transformed by a variety of transition metal and lanthanide systems. Although the C–H bond is weaker than the C–F bond regardless of the hybridization of the carbon, the reaction of the C–F bond at the metal is usually more exothermic than the corresponding reaction of the C–H bonds. Both bonds are activated by the metal systems, but the preference for activating these bonds depends on the nature of the hydrocarbon and of the metal system, so that the reaction can be directed exclusively toward C–H or C–F bonds or yield a mixture of products. Additionally, the presence of fluorine differentiates between C–H bonds at different positions resulting in regioselective C–H bond activation; paradoxically, the strongest C–H bond reacts preferentially. The purpose of this review is to describe the field of reactions of partially fluorinated substrates with transition metal atoms, ions, and molecular complexes. The controlling physical properties (thermodynamics and kinetics) are described first, followed by a description of stoichiometric reactions, with the competition between the C–H and C–F activations as focus. A few representative catalytic systems are discussed. The review also highlights the benefit of combining experimental and theoretical studies.

中文翻译：

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C–H活化的选择性以及在碳氟化合物上C–H和C–F键活化之间的竞争

部分氟化的烷烃，芳烃和烯烃可以通过多种过渡金属和镧系元素进行转化。尽管无论碳原子如何杂化，C–H键都比C–F键弱，但金属上C–F键的反应通常比C–H键的反应放热。两个键都被金属系统激活，但是激活这些键的优先级取决于烃和金属系统的性质，因此反应可以专门针对C–H或C–F键或生成混合物产品。此外，氟的存在会在不同位置的C–H键之间区分开，从而导致区域选择性C–H键活化。矛盾的是，最强的CH键优先发生反应。这篇综述的目的是描述部分氟化的底物与过渡金属原子，离子和分子络合物的反应领域。首先描述了控制物理性质（热力学和动力学），然后描述化学计量反应，重点是C–H和C–F活化之间的竞争。讨论了一些代表性的催化体系。该评论还强调了将实验研究与理论研究相结合的好处。讨论了一些代表性的催化体系。该评论还强调了将实验研究与理论研究相结合的好处。讨论了一些代表性的催化体系。该评论还强调了将实验研究与理论研究相结合的好处。