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Formation, Expansion, and Interconversion of Metallarings in a Sulfur‐Bridged Au I Co III Coordination System
Author(s) -
Oji Katsuya,
IgashiraKamiyama Asako,
Yoshinari Nobuto,
Konno Takumi
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201309986
Subject(s) - chemistry , sulfur , lability , crystallography , solvent , medicinal chemistry , stereochemistry , organic chemistry
A novel Au I Co III 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 Au I is reported. Complex 1 − acts as a sulfur‐donating metallaligand and reacts with the gold(I) precursor to give [Au 2 Co 2 ( D ‐nmp) 4 ] ( 2 ), which has an eight‐membered Au I 2 Co III 2 metallaring. Treatment of 2 with [Au 2 (dppe) 2 ] 2+ (dppe=1,2‐bis(diphenylphosphino)ethane) leads to the formation of [Au 4 Co 2 (dppe) 2 ( D ‐nmp) 4 ] 2+ ( 3 2+ ), which consists of an 18‐membered Au I 4 Co III 2 metallaring that accommodates a tetrahedral anion (BF 4 − , ClO 4 − , ReO 4 − ). In solution, the metallaring structure of 3 2+ is readily interconvertible with the nine‐membered Au I 2 Co III metallaring structure of [Au 2 Co(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 AuS and AuP bonds, which is essential for metallaring expansion and contraction.