Advances in the Reactivity of Amido-Bridged Binuclear Carbonylruthenium Complexes – Derivative Chemistry of the Cationic Complex [Ru2(μ-dan)(μ-H)(CO)6][BF4] (H2dan = 1,8-Diaminonaphthalene)
✍ Scribed by Javier A. Cabeza; Jorge García-Díez; Víctor Riera
- Publisher
- John Wiley and Sons
- Year
- 1998
- Tongue
- English
- Weight
- 164 KB
- Volume
- 1998
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
The reactivity of the cationic amido-bridged binuclear transformed into the asymmetric isomer 7b under thermal conditions (70 °C, 10 h) or under acid catalysis ([HOEt 2 ][BF 4 ], ruthenium carbonyl complex [Ru 2 (µ-dan)(µ-H)(CO) 6 ] + (H 2 dan = 1,8-diaminonaphthalene) (2) with some anionic and 18 °C, 1 min). Such isomerization reactions can be prevented by adding an excess of triphenylphoshane to the solutions. neutral nucleophilic reagents has been investigated. The reaction of 2 with halide anions gives neutral products,
The complexes 7a and 7b can also be prepared by treating the neutral complex [Ru 2 (µ-dan)(PPh 3 ) 2 (CO) 4 ] with [Ru 2 X(µ-dan)(µ-H)(CO) 5 ] [X = Cl (3), Br (4), I (5)], which result from the regiospecific substitution of the halide anion [HOEt 2 ][BF 4 ] in the presence (for 7a) or in the absence (for 7b) of triphenylphoshane. In addition, compound 3 reacts for one of the CO ligands trans to the bridging hydride. Compound 3 is more conveniently prepared by treatment of with triphenylphoshane at room temperature to give the symmetric cationic complex 7a , whereas the reaction of the neutral complex [Ru 2 (µ-dan)(CO) 6 ] with gaseous hydrogen chloride. The reaction of 2 with tri-complex 5 with triphenylphoshane requires higher temperature and gives the asymmetric isomer 7b. phenylphosphane affords the disubstituted product of C 2v symmetry [Ru 2 (µ-dan)(µ-H)(PPh 3 ) 2 (CO) 4 ] + (7a), which can be