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GroupII metal complexes of the germylidendiide dianion radical and germylidenide anion

Chia, S. P., Carter, Emma, Xi, H., Li, Y. and So, C. W. 2014. GroupII metal complexes of the germylidendiide dianion radical and germylidenide anion. Angewandte Chemie 53 (32) , pp. 8455-8458. 10.1002/anie.201404357

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The two-electron reduction of a Group 14-element(I) complex [RË⋅] (E=Ge, R=supporting ligand) to form a novel low-valent dianion radical with the composition [RË:]. 2− is reported. The reaction of [LGeCl] (1, L=2,6-(CH[DOUBLE BOND]NAr)2C6H3, Ar=2,6-iPr2C6H3) with excess calcium in THF at room temperature afforded the germylidenediide dianion radical complex [LGe]. 2−⋅Ca(THF)32+ (2). The reaction proceeds through the formation of the germanium(I) radical [LGe⋅], which then undergoes a two-electron reduction with calcium to form 2. EPR spectroscopy, X-ray crystallography, and theoretical studies show that the germanium center in 2 has two lone pairs of electrons and the radical is delocalized over the germanium-containing heterocycle. In contrast, the magnesium derivative of the germylidendiide dianion radical is unstable and undergoes dimerization with concurrent dearomatization to form the germylidenide anion complex [C6H3-2-{C(H)[DOUBLE BOND]NAr}Ge-Mg-6-{C(H)-NAr}]2 (3).

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: Wiley-Blackwell
ISSN: 0044-8249
Last Modified: 25 Feb 2019 14:00

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