Substitution of carbonyl ligands in [Ru10C2(CO)24]2- (1) by allene (1,2-propadiene) proceeds cleanly in diglyme at 90°C (1 atm) to afford the monoallene derivative [Ru10C2(CO)22(μ-η2: η2-C3H4)]2- (2). Treatment of either 1 or 2 with allene at 140°C (1 atm) forms the disubstituted derivative [Ru10C2(CO)20(μ-η2:η 2-C3H4)2]2- (3) in high yield. The new clusters have been isolated as salts with [PPN]+ or [PPh3CH2CH2PPh3]2+ counterions and have been characterized by analytical, spectroscopic, and X-ray crystallographic methods. The framework structures of both molecular cluster anions 2 and 3 are based on edge-shared bioctahedra, with the allene ligands bridging one or two pairs of apical positions, respectively. The idealized symmetries are C2 for 2 and D2 for 3. The solution structures and dynamics of 2 and 3 have been studied by 13C NMR spectroscopy, including variable-temperature and 13C-13C COSY experiments.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry