期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 43, 页码 23274-23280出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202108146
关键词
anagostic interactions; gold; iron; silicon; zwitterionic complexes
资金
- WACKER Chemie AG
- European Research Council [SILION 63794]
- Projekt DEAL
The facile synthesis of the first bis-N-heterocyclic imine-stabilized chlorosilyliumylidene and its consecutive reaction with PPh3AuCl and K2Fe(CO)(4) resulted in the formation of a unique heterobimetallic complex. The complex bears an unusual linear Si-Au-Fe structure with a rare anagostic interaction between the gold atom and a CH bond. Computational analysis shows strong hyperconjugative back donation from the gold(I) atom to the silyliumylidene ligand.
The facile synthesis of the first bis-N-heterocyclic imine-stabilized chlorosilyliumylidene 1 is reported. Remarkably, consecutive reaction of 1 with PPh3AuCl and K2Fe(CO)(4) gives rise to the unique heterobimetallic complex 1,2-((NHI)-N-Mes)(2)-C2H4-ClSiAuFe(CO)(4) (4). The overall neutral complex 4 bears an unusual linear Si-Au-Fe structure and a rare anagostic interaction between the d(10)-configured gold atom and a CH bond of the mesityl ligand. According to the computational analysis and Fe-57 Mossbauer spectroscopy, the formal Fe-oxidation state remains at -II. Thus, the electronic structure of 4 is best described as an overall neutral-yet zwitterionic-heterobimetallic Si(II)(+)-Au(I)(+)-Fe(-II)(2-)-silyliumylidene complex, derived from double anion exchange. The computational analysis indicates strong hyperconjugative back donation from the gold(I) atom to the silyliumylidene ligand.
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