Formation,Expansion, and Interconversion of Metallarings in a Sulfur‐Bridged AuICoIII Coordination System |
| |
| Authors: | Katsuya Oji Dr Asako Igashira‐Kamiyama Dr Nobuto Yoshinari Prof Takumi Konno |
| |
| Institution: | 1. Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560‐0043 (Japan);2. CREST‐JST, Toyonaka, Osaka 560‐0043 (Japan) |
| |
| Abstract: | A novel AuICoIII coordination system that is derived from the newly prepared Co(D ‐nmp)2]? ( 1 ?; D ‐nmp=N‐methyl‐D ‐penicillaminate) and a gold(I) precursor AuI is reported. Complex 1 ? acts as a sulfur‐donating metallaligand and reacts with the gold(I) precursor to give Au2Co2(D ‐nmp)4] ( 2 ), which has an eight‐membered AuI2CoIII2 metallaring. Treatment of 2 with Au2(dppe)2]2+ (dppe=1,2‐bis(diphenylphosphino)ethane) leads to the formation of Au4Co2(dppe)2(D ‐nmp)4]2+ ( 3 2+), which consists of an 18‐membered AuI4CoIII2 metallaring that accommodates a tetrahedral anion (BF4?, ClO4?, ReO4?). In solution, the metallaring structure of 3 2+ is readily interconvertible with the nine‐membered AuI2CoIII metallaring structure of Au2Co(dppe)(D ‐nmp)2]+ ( 4 +); this process depends on external factors, such as solvent, concentration, and nature of the counteranion. These results reveal the lability of the Au? S and Au? P bonds, which is essential for metallaring expansion and contraction. |
| |
| Keywords: | heterometallic complexes metallacycles ring expansion S ligands template synthesis |
|
|
