Unprecedented bis(silylene)-supported silylone–metal complexes with Si<sup>0</sup>→Cu<sup>I</sup>, Si<sup>0</sup>→Ni<sup>I</sup>, and Si<sup>0</sup>→Ni<sup>II</sup> dative bonds
The first silylone-3d-metal complexes, LSiCu(NacNac<sup>M</sup>) (2) [L = 1,2-(RSi)<sub>2</sub>-1,2-C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>, R = PhC(N<i>t</i>Bu)<sub>2</sub>; NacNac<sup>M</sup> = HC(CMeNMes)<sub>2</sub>, Mes = 2,4,6-Me<sub>3</sub>-C<sub>6</sub>H<sub>2</sub>] and LSiNi(NacNac<sup>D</sup>) (3) [NacNac<sup>D</sup> = HC(CMeNDipp)<sub>2</sub>, Dipp = 2,6-iPr<sub>2</sub>-C<sub>6</sub>H<sub>3</sub>], are reported, resulting from the reaction of the strongly σ-donating and chelating bis(silylenyl)-<i>ortho</i>-carborane silylone LSi<sup>0</sup> with [(NacNac<sup>M</sup>Cu)<sub>2</sub>benzene] and [(NacNac<sup>D</sup>Ni)<sub>2</sub>toluene], respectively. Density Functional Theory (DFT) analyses reveal that complex 2 features a Si<sup>0</sup>→Cu<sup>I</sup> dative bond, while 3 exhibits a Si<sup>0</sup>→Ni<sup>I</sup> bond. Oxidation of the Si<sup>0</sup>-Ni<sup>I</sup> species 3 with [Cp<sub>2</sub>Fe]<sup>+</sup> occurs at the Ni site to form the [3]<sup>+</sup> cation with a Si<sup>0</sup>→Ni<sup>II</sup> coordination.
Authors
- Jun Zhu (ORCID: https://orcid.org/0000-0002-2099-3156)
- Changkai Shan
- Matthias Drieß (ORCID: https://orcid.org/0000-0002-9873-4103)
- Shenglai Yao (ORCID: https://orcid.org/0000-0002-4005-835X)
- Chenshu Dai
Institutions
- Lishui University (CN)
- Chinese University of Hong Kong, Shenzhen (CN)
- Technische Universität Berlin (DE)
Publication Details
- Journal
- Chemical Communications
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5cc02098k
- Primary Topic
- Synthesis and characterization of novel inorganic/organometallic compounds
- Type
- article
- Field-Weighted Citation Impact
- 0.00