Institut Charles Gerhardt, UMR 5253 CNRS Université Montpellier , cc 1501, Place E. Bataillon, 34095 Montpellier, France.
Centre for Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Oslo , P.O. Box 1033, Blindern, 0315 Oslo, Norway.
Chem Rev. 2017 Jul 12;117(13):8710-8753. doi: 10.1021/acs.chemrev.7b00163. Epub 2017 Jun 27.
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.
部分氟化的烷烃、芳烃和烯烃可以通过各种过渡金属和镧系元素体系进行转化。尽管无论碳的杂化如何，C-H 键都比 C-F 键弱，但金属上的 C-F 键的反应通常比相应的 C-H 键反应更放热。这两种键都被金属体系激活，但对这些键进行激活的偏好取决于碳氢化合物和金属体系的性质，因此反应可以专门针对 C-H 或 C-F 键进行，或者产生混合物产物。此外，氟的存在区分了不同位置的 C-H 键，导致区域选择性的 C-H 键活化；矛盾的是，最强的 C-H 键优先反应。本综述的目的是描述部分氟化底物与过渡金属原子、离子和分子配合物的反应领域。首先描述控制物理性质（热力学和动力学），然后描述化学计量反应，重点关注 C-H 和 C-F 活化之间的竞争。讨论了一些有代表性的催化体系。该综述还强调了结合实验和理论研究的好处。
