累积2c-2e vs 3c-2e π-Back供主：锗烯金(I)配合物的构象偏好

IF 6.1 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers Pub Date : 2025-04-24 DOI:10.1039/d5qi00539f

Lifang Wu, Zhang Rong, Xinran Wang, Wenyao Zeng, Lanhui Zhang, Yining Gao, Jiyong Liu, Lingbing Kong, Jiaxin Chen, Liliang Wang

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引用次数: 0

摘要

首次合成了同色和异色阳离子锗金配合物3、4和7，并对其结构进行了表征，同时发现了新型的π-背给体。这些配合物表现出不同的构象偏好（垂直或准平面），由乙烯和NHC配体的π-酸度调节。我们的键合分析进一步表明，同色络合物3表现出惊人的累积两中心-两电子(2c-2e) π-背供价，而异色络合物4和7表现出惊人的三中心-两电子(3c-2e) π-背供价。这些发现为广泛π-体系的非典型破坏以及从准平面构象到垂直构象的转变提供了一个全面的解释。

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Cumulative 2c-2e vs 3c-2e π-Back Donations: Conformation Preferences in Germylene Gold(I) Complexes

The first homoleptic and heteroleptic cationic germylene-gold(I) complexes 3, 4, and 7 have been synthesized and structurally characterized, accompanied by the discovery of novel types of π-back donations. These complexes exhibit distinct conformation preferences (vertical vs quasi-planar) modulated by the π-acidity of germylene and NHC ligands. Our bonding analyses further indicated that the homoleptic complex 3 exhibits marvelous cumulative two-center-two-electron (2c-2e) π-back donations, whereas the heteroleptic complexes 4 and 7 demonstrate extraordinary three-center-two-electron (3c-2e) π-back donations. These findings offer a comprehensive explanation for the atypical disruption of extensive π-systems, along with the transition from quasi-planar to vertical conformations.

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