10.1002/anie.202009359
Angewandte Chemie International Edition
RESEARCH ARTICLE
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as the analogous reductive elimination in the case of a
monoligated (PPh3)AuArCN2 complex (Ar
=
2,6-F2-C6H3)
proceeds exclusively under thermal conditions (above 60 ºC) over
long periods of time.[15] As for the more electron-deprived complex
3f, the C(sp2)-C(sp) bond formation only occurred when the
temperature is raised to 50 °C (Scheme 3b). In an analogous
manner, the reaction of complexes 3a and 3c with
methylpropiolate delivered the products of C(sp2)-C(sp) reductive
elimination 8a and 8c at ambient temperature in excellent yields.
Interestingly, more electron-rich alkynes such as 1-ethynyl-(3,5-
bistrifluoromethyl)benzene and phenylacetylene also delivered
the corresponding cross-coupling products 9a and 10a in 53 and
72% yield, respectively (Scheme 3c). In this case, the quantitative
formation (MeDalPhos)gold(I)-acetylide 7/HSbF6 after reaction
completion could be again confirmed through its independent
preparation by reaction of (MeDalPhos)gold(I) acetate with
methylpropiolate. [8] These results are in line with those of the well-
established C(sp2)-C(sp2) and C(sp3)-C(sp3) bond formation in
phosphine ligated systems.[16]
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Conclusion
Herein, we successfully synthesized, isolated and characterized
a new family of stable bidentate (P^N)arylgold(III) fluoride
complexes. Crystallographic and computational DFT analysis
revealed a significant ionic character of the Au-F bond which
correlates to the geometry distortion induced by the ligand. These
complexes, featuring an unprecedented P-Au-F system, were
able to activate C(sp) ligands such as methylpropiolate and
TMSCN enabling the study of the corresponding C(sp2)-C(sp)
reductive elimination. This reaction proceeds under mild reaction
conditions at higher rates than those reported for analogous
phosphine-based monodentate systems, thus highlighting the
potential of this work to develop and/or improve existing
gold(I)/gold(III) catalytic methods for the cross coupling of C(sp2)-
C(sp) bonds.
[5]
Acknowledgements
We thank the European Research Council (ERC Starting grant
agreement no. 307948) and the Swiss National Science
Foundation (SNF 200020_146853) for financial support.
Keywords: gold(III) • fluoride • ligand exchange • reductive
elimination
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