Journal
ACS CATALYSIS
Volume 10, Issue 14, Pages 7934-7944Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.0c01301
Keywords
inorganic chemistry; organic chemistry; catalysis; organometallics; Kumada cross-coupling; C-F activation; heterobimetallic catalysis
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Funding
- National Institute of General Medical Sciences (NIGMS) of the National Institutes of Health (NIH) [R35GM128794]
- Charles E. Kaufman Foundation of The Pittsburgh Foundation [KA2016-85227]
- National Science Foundation [CHE-1902509]
- Petroleum Research Fund [PRF 59570-ND1]
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Herein is described a mechanistic study of a palladium-catalyzed cross-coupling of aryl Grignard reagents to fluoroarenes that proceeds via a low-energy heterobimetallic oxidative addition pathway. Traditional oxidative additions of aryl chlorides to Pd complexes are known to be orders of magnitude faster than with aryl fluorides, and many palladium catalysts do not activate aryl fluorides at all. The experimental and computational studies outlined herein, however, support the view that at elevated Grignard/ArX ratios (i.e., 2.5:1), a Pd-Mg heterobimetallic mechanism predominates, leading to a remarkable decrease in the energy required for Ar-F bond activation. The heterobimetallic transition state for the C-X bond cleavage is proposed to involve simultaneous Pd backbonding to the arene and Lewis acid activation of the halide by Mg to create a low-energy transition state for oxidative addition. The insights gained from this computational study led to the development of a phosphine ligand that was shown to be similarly competent for Ar-F bond activation.
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