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Updated: Dec 17, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Synthesis, Structure, Reactivity and Catalytic Implications of a Cationic, Acetylide-Bridged Trigold-JohnPhos Species
Abdessamad Grirrane1, Eleuterio Álvarez2, Hermenegildo García1
1Instituto Universitario de Tecnología Química CSIC-UPV, Universitat Politècnica de València, Av. de los Naranjos s/n, 46022, Valencia, Spain.
Abstract:
The cationic complex [(JohnPhos-Au)3 (acetylide)][SbF6 ] (JohnPhos=(2-biphenyl)di-tert-butylphosphine, L1) has been characterised structurally and features an acetylide-trigold(I)-JohnPhos system; the trinuclear-acetylide unit, coordinated to the monodentate bulk phosphines, adopts an unprecedented μ,η1 ,η2 ,η1 coordination mode with an additional interaction between distal phenyl rings and gold centres. Other cationic σ,π-[(gold(I)L1)2 ] complexes have also been isolated. The reaction of trimethylsilylacetylene with various alcohols (iPrOH, nBuOH, n-HexOH) catalysed by cationic [AuI L1][SbF6 ] complexes in CH2 Cl2 at 50 °C led to the formation of acetaldehyde acetals with a high degree of chemo- and regioselectivity. The reaction mechanism was studied, and several organic and inorganic intermediates have been characterised. A comparative study with the analogous cationic [CuI L1][PF6 ] complex revealed different behaviour; the copper metal is lost from the coordination sphere leading to the formation of cationic vinylphosphonium and copper nanoparticles. Additionally, a new catalytic approach for the formation of this high-value cationic vinylphosphonium has been established.
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