10.1002/anie.201906005
Angewandte Chemie International Edition
COMMUNICATION
This work was supported by the National Science Foundation
under Award Number DMR-1420073. J.D. is supported by the
Margaret and Herman Sokol Fellowship and the Ted Keusseff
Fellowship. T.D. is a recipient of the Alfred P. Sloan Research
Fellowship (FG-2018-10354) and the Camille-Dreyfus Teacher-
Scholar Award (TC-19-019). C.T.H. acknowledges the support of
the National Science Foundation (NSF) Chemistry Research
Instrumentation and Facilities Program (CHE-0840277) and
Materials Research Science and Engineering Center (MRSEC)
Program (DMR-1420073).
In summary, the direct reduction of (tBu-Xantphos)Ni(II)Br2 by
Zn generates (tBu-Xantphos)Ni(I)Br. (tBu-Xantphos)Ni(I)–Me and
(tBu-Xantphos)Ni(I)–Et complexes undergo fast insertion of CO2
at 22 ºC, whereas (tBu-Xantphos)Ni(I)–phenyl, acetylide, and
phenoxide complexes gave no insertion products. This
observation represents the first characterization of CO2 insertion
into Ni(I)-alkyl bonds and verifies the nucleophilic addition
mechanism proposed by previous DFT calculations. The fast
reaction rate corroborates the facile catalytic reactions and the
predicted importance of Ni(I) intermediates relative to Ni(II) in
carboxylation. Characterization of these stoichiometric reactions
provides evidence to support mechanistic proposals for Ni-
catalyzed carboxylation reactions of organic and organometallic
reagents.
Keywords: Ni(I) • CO2 • insertion • Ni-carboxylate • reaction
intermediate
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