Selectivity of C-H activation and competition between C-H and C-F bond activation at fluorocarbons

TY - JOUR

T1 - Selectivity of C-H activation and competition between C-H and C-F bond activation at fluorocarbons

AU - Eisenstein, Odile

AU - Milani, Jessica

AU - Perutz, Robin N.

N1 - © 2017 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details

PY - 2017/7/12

Y1 - 2017/7/12

N2 - 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 reaction 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

AB - 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 reaction 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

UR - http://www.scopus.com/inward/record.url?scp=85024111836&partnerID=8YFLogxK

U2 - 10.1021/acs.chemrev.7b00163

DO - 10.1021/acs.chemrev.7b00163

M3 - Review article

AN - SCOPUS:85024111836

SN - 0009-2665

VL - 117

SP - 8710

EP - 8753

JO - Chemical Reviews

JF - Chemical Reviews

IS - 13

ER -