Structure and reactivity of germylene-bridged digold complexes

Liliang Wang, Guorong Zhen, Yinhuan Li, Mitsuo Kira (), Liping Yan, Xiao-Yong Chang (), Lu Huang and Zhifang Li ()
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Liliang Wang: Hangzhou Normal University
Guorong Zhen: Hangzhou Normal University
Yinhuan Li: Hangzhou Normal University
Mitsuo Kira: Hangzhou Normal University
Liping Yan: Hangzhou Normal University
Xiao-Yong Chang: Southern University of Science and Technology
Lu Huang: Hangzhou Normal University
Zhifang Li: Hangzhou Normal University

Nature Communications, 2022, vol. 13, issue 1, 1-9

Abstract: Abstract The bonding between gold and main-group metallic elements (M) featuring Auδ−−Mδ+ polarity, has been studied recently. The gold in the bonds is expected to have the oxidation number of −1, and hence, nucleophilic. However, the knowledge of the reactivity of the gold-metal bonds remains limited. Here, we report digold-substituted germanes of the form of R’2Ge(AuPR3)(AuGeR’2) (3a; R = Me, 3b; R = Et), featuring two Au-Ge(IV) and one Au-Ge(II) bonds. DFT calculations of 3a revealed the existence of high-lying σ(Ge-Au) type HOMO and low-lying LUMO with germylene pπ nature. A pendular motion of AuPR3 group between Ge(IV) and Ge(II) of 3 occurs in the NMR time scale, suggesting that the Ge(II) center has an enhanced electrophilicity to be attacked by the nucleophilic gold (−I) atom. 3a reacts with nucleophilic Cl− and electrophilic MeOTf reagents at Ge(II) and Ge(IV) centers, respectively.

Date: 2022
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DOI: 10.1038/s41467-022-29476-1

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