10.1002/anie.201901866
Angewandte Chemie International Edition
COMMUNICATION
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Scheme 6. Comparison of precatalysts in a prototypical (a) cross-
electrophile coupling; and (b) decarboxylative Csp2-Csp3 coupling.
Conditions for each reaction are given in the SI. aFormed in situ, see SI.
the NiI intermediates proposed in cross-electrophile and
decarboxylative coupling are active in catalysis.
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In summary, we have shown that paramagnetic bidentate
polypyridyl-ligated Ni species can be formed through sequences
involving catalytically-relevant elementary steps. The nuclearity of
the paramagnetic complexes is a function of the ligand, and it is
possible that dimeric species are present in catalysis. Further, in
the case of dtbbpy ligated complexes, we suggest that the ligand
can act as an electron reservoir, which may be related to the high
catalytic activity of these species. Some of our new paramagnetic
species undergo elementary reactions proposed in cross-
electrophile or decarboxylative coupling and depending on the
ancillary ligand they are catalytically active for these reactions.
Overall, this work provides information about highly reactive
paramagnetic intermediates which may help the design of more
efficient systems for Csp2-Csp3 coupling.
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