Structure and reactivity of germylene-bridged digold complexes

Liliang Wang; Guorong Zhen; Yinhuan Li; Mitsuo Kira; Liping Yan; Xiao-Yong Chang; Lu Huang; Zhifang Li

doi:10.1038/s41467-022-29476-1

Structure and reactivity of germylene-bridged digold complexes

Nat Commun. 2022 Apr 4;13(1):1785. doi: 10.1038/s41467-022-29476-1.

Authors

Liliang Wang¹, Guorong Zhen¹, Yinhuan Li¹, Mitsuo Kira², Liping Yan¹, Xiao-Yong Chang³, Lu Huang¹, Zhifang Li⁴

Affiliations

¹ College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, People's Republic of China.
² College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, People's Republic of China. mitsuo.kira.e2@tohoku.ac.jp.
³ Department of Chemistry, Southern University of Science and Technology, 518055, Shenzhen, Guangdong, People's Republic of China. changxy@sustech.edu.cn.
⁴ College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, People's Republic of China. zhifanglee@hznu.edu.cn.

Abstract

The bonding between gold and main-group metallic elements (M) featuring Au^δ--M^δ+ 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 p_π 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.