A nucleophilic gold complex
Hicks, J., Mansikkamäki, A., Vasko, P., Goicoechea, J. M., & Aldridge, S. (2019). A nucleophilic gold complex. Nature Chemistry, 11(3), 237-241. https://doi.org/10.1038/s41557-018-0198-1
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2019Copyright
© 2019, Springer Nature
Solid-state auride salts featuring the negatively charged Au– ion are known to be stable in the presence of alkali metal counter-ions. While such electron-rich species might be expected to be nucleophilic (cf. I– ), their instability in solution means that this has not been verified experimentally. Here we report the two-coordinate gold complex (NON)AlAuPtBu3 (3, NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene) synthesised by the reaction of the potassium aluminyl complex [K{Al(NON)}]2 (1) with tBu3PAuI, and which features a strongly polarized bond, Au(d-)–Al(d+). 3 has been studied computationally, with QTAIM charge analysis implying a charge at gold (-0.82) which is in line with the relative electronegativities of the two metals (Au: 2.54; Al: 1.61 on the Pauling scale). Consistently, 3 is found to act as an unprecedented nucleophilic source of gold, reacting with diisopropylcarbodiimide and CO2 to give the Au–C bonded insertion products (NON)Al(X2C)AuPtBu3 (X = NiPr, 4; X = O, 5).
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1755-4330Publication in research information system
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