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comparison, the same procedure was performed for AgBF
4
,
[2]
For early studies involving the intermediacy of C-X oxidative addition
processes to gold(I) see: a) A. Tamaki, L. K. Kochi, J. Organomet.
Chem. 1972, 40, C81; b) A. Johnson, R. J. Puddephatt, Inorg. Nucl.
Chem. Lett. 1973, 9, 1175; c) A. Tamaki, J. K. Kochi, J. Organomet.
Chem. 1973, 64, 411; d) A. Johnson, R. J. Puddephatt, J. Organomet.
Chem. 1975, 85, 115; e) A. Shiotani, H. Schmidbaur, J. Organomet.
Chem. 1972, 37, C24; f) A. Tamaki, S. A. Magennis, J. K. Kochi, J. Am.
Chem. Soc. 1973, 95 6487; g) M. T. Johnson, J. M. J van Rensburg, M.
Axelsson, M. S. G. Ahlquist, O. F. Wendt, Chem. Sci. 2011, 2, 2373; h)
M. D. Levin, F. D. Toste, Angew. Chem. Int. Ed. 2014, 53, 6211; i) R.
Cai, M. Lu, E. Y. Aguilera, Y. Xi, N. G. Akhmedov, J. L. Petersen, H.
Chen, X. Shi, Angew. Chem. Int. Ed. 2015, 54, 8772; j) J. Serra, C. J.
Whiteoak, F. Acuꢀa-Parꢁs, M. Font, J. M. Luis, J. Lloret-Fillol, X. Ribas,
J. Am. Chem. Soc. 2015, 137, 13389.
which gave a Δδ value of 8.2. These results indicate that
[3]
M. Joost, A. Amgoune, D. Bourissou, Angew. Chem. Int. Ed. 2015, 54,
1
5022.
gold(III) complexes 3 could find applications as Lewis acid
catalysts. Moreover, the ability of the photoredox-promoted
oxidative addition method to provide a range of electronically-
varied gold(III) complexes for investigation could prove useful as
a tool for allowing the systematic study of the organometallic
chemistry of gold(III).
[
4]
5]
S. G. Bratsch, J. Phys. Chem. Ref. Data 1989, 18, 1.
[
Selected references: a) N. P. Mankad, F. D. Toste, J. Am. Chem. Soc.
2010, 132, 12859; b) P. de Frémont, R. Singh, E. D. Stevens, J. L.
Petersen, S. P. Nolan, Organometallics 2007, 26, 1376; c) S. Gaillard,
M. A. Z. Slawin, A. T. Bonura, E. D. Stevens, S. P. Nolan,
Organometallics 2010, 29, 394; d) M. Hofer, C. Nevado, Eur. J. Inorg.
Chem. 2012, 1338; e) R. Usón, A. Laguna, J. Pardo, Synth. React.
Inorg. Met. Org. Chem. 1974, 4, 499; f) D. Schneider, A. Schier, H.
Schmidbaur, Dalton. Trans. 2004, 1995; g) D. Schneider, O. Schuster,
H. Schmidbaur, Dalton. Trans. 2005, 1940; h) A. Johnson, R.
Puddephatt, J. Chem. Soc., Dalton Trans. 1976, 1360; i) M. S. Winston,
W. J. Wolf, F. D. Toste, J. Am. Chem. Soc. 2014, 136, 7777; j) R. D.
Sanner, J. H. Satcher, M. W. Droege, Organometallics 1989, 8, 1498;
k) J. Gil-Rubio, J. Vicente, Dalton. Trans. 2015, 44, 19432.
Figure 3. Molecular structure of complex 5aa in the solid state. Ellipsoids set
at 30% probability (CCDC 1483280).
In conclusion, we have developed a visible light-promoted
photoredox method for the oxidative addition of aryldiazonium
salts to gold(I) complexes. This process not only provides direct
experimental evidence for the involvement of such steps in dual
gold/photoredox catalysis but also serves as a fast and
straightforward method to access well-defined gold(III)
complexes. Using this novel strategy, we successfully prepared
[6]
a) P. Schwerdtfeger, H. L. Hermann, H. Schmidbaur, Inorg. Chem.
2003, 42, 1334; b) M. A. Carvajal, J. J. Novoa, S. Alvarez, J. Am. Chem.
Soc. 2004, 126, 1465; c) M. Livendahl, C. Goehry, F. Maseras, M. A.
Echavarren, Chem. Commun. 2014, 50, 1533; d) I. Fernández, L. P.
Wolters, F. M. Bickelhaupt, J. Comp. Chem. 2014 , 35 , 2140.
T. Lauterbach, M. Livendahl, A. Rosellon, P. Espinet, A. M. Echavarren,
Org. Lett. 2010, 12, 3006.
[
7]
8]
(
C,N)-cyclometalated gold(III) species bearing a variety of
phosphine and N-heterocyclic carbene ligands. Subsequent
abstraction of the chloride delivered dicationic species, which
display Lewis acid behavior. The remarkably mild reaction
conditions and broad scope of ligands suggest that this method
could be a useful synthetic tool that enables the systematic
study of the properties and reactivity of gold(III) species.
[
a) M. Joost, A. Zeineddine, L. Estévez, S. Mallet−Ladeira, K. Miqueu,
A. Amgoune, D. Bourissou, J. Am. Chem. Soc. 2014, 136, 14654; b) L.
Estévez, K. Miqueu, A. Amgoune, D. Bourissou, Angew. Chem. Int. Ed.
2015, 54, 5236.
[
9]
C.-Y. Wu, T. Horibe, C. J. Borch, F. D. Toste, Nature 2015, 517, 449.
[
10] Selected reviews on visible light photoredox catalysis: a) T. P. Yoon, M.
A. Ischay, J. Du, Nat. Chem. 2010, 2, 527; b) J. M. R. Narayanam, C. R.
J. Stephenson, Chem. Soc. Rev. 2011, 40, 102; c) J. Xuan, W.-J. Xiao,
Angew. Chem. Int. Ed. 2012, 51, 6828; d) C. K. Prier, D. A. Rankic, D.
W. C. MacMillan, Chem. Rev. 2013, 113, 5322; e) D. M. Schultz, T. P.
Yoon, Science, 2014, 343, 1239176; f) M. N. Hopkinson, B. Sahoo, J.-L.
Li, F. Glorius, Chem.–Eur. J. 2014, 20, 3874; g) M. D. Levin, S. Kim, F.
D. Toste, ACS Cent. Sci. 2016, 2, 293.
Scheme 4. Lewis acid measurements using the Gutmann-Beckett method.
[
11] a) B. Sahoo, M. N. Hopkinson, F. Glorius, J. Am. Chem. Soc. 2013, 135,
5505; b) M. N. Hopkinson, B. Sahoo, F. Glorius, Adv. Synth. Catal.
2
014, 356, 2794; c) A. Tlahuext-Aca, M. N. Hopkinson, B. Sahoo, F.
Acknowledgements
Glorius, Chem. Sci. 2016, 7, 86; d) A. Tlahuext-Aca, A., M. N.
Hopkinson, R. A. Garza-Sanchez, F. Glorius, Chem. Eur. J., 2016, 22,
5909; e) X.-Z. Shu, M. Zhang, Y. He, H. Frei, F. D. Toste, J. Am. Chem.
Soc. 2014, 136, 5844; f) Y. He, H. Wu, F. D. Toste, Chem. Sci. 2015, 6,
We thank M. Teders, Dr. A. Gómez-Suárez, Steffen Greßies and
M. Stangier (WWU Münster) for experimental assistance and
helpful discussions. Generous financial support by the NRW
Graduate School of Chemistry (A. T. A.), the Alexander von
Humboldt Foundation (M. N. H.) and the Deutsche
Forschungsgemeinschaft (Leibniz Award) are gratefully
acknowledged.
1194; g) Y. He, H. Wu, F. D. Toste, Chem. Sci. 2015, 6, 1194; h) S.
Kim, J. Rojas-Martin, F. D. Toste, Chem. Sci. 2016, 7, 85; i) D. V. Patil,
H. Yun, S. Shin, Adv. Synth. Catal. 2015, 357, 2622; j) J. Um, H. Yun, S.
Shin, Org. Lett. 2016, 18, 484.
[
[
12] During the preparation of this manuscript, reports by the Hashmi group
on visible light-promoted gold catalysis and the synthesis of
organometallic gold(III) complexes in the absence of a photocatalyst
appeared: a) K. Huang, M. Rudolph, F. Rominger, A. S. K. Hashmi,
Angew. Chem. Int. Ed. 2016, 55, 4808; b) L. Huang, F. Rominger, M.
Rudolph, A. S. K. Hashmi, Chem. Commun. 2016, 52, 6435.
Keywords: Gold(III) Complexes • Photoredox Catalysis •
Oxidative Addition • Diazonium Salts
13] Selected examples: a) F. Mohr, Gold Chemistry: Applications and
Future Directions in the Life Sciences: Highlights and Future Directions,
Wiley Interscience: New York, 2009; b) A. S. K. Hashmi, G. J. Hutching,
Angew. Chem. Int. Ed. 2006, 45, 7896; c) A. S. K. Hashmi, Chem. Rev.
[
1]
R. H. Crabtree, The Organometallic Chemistry of the Transition Metals,
Wiley Interscience, New York, 2005.