Abstract
Tribenzylphosphane sulfide (SPBn3) reacts with [Cu(CH3CN)4]PF6 in a 2:1 ratio to give [Cu(CH3CN)(SPBn3)2]PF6 whereas with [Ag(CH3CN)4]PF6 in the same ratio it forms [Ag2(SPBn3)3](PF6)2. The crystal structure of the Cu(I) complex shows it to contain discrete 3-coordinate [Cu(CH3CN)(SPBn3)2]+ cations and [PF6]− anions with the Cu atom lying in the plane formed by the two coordinated sulfur atoms and the nitrogen from the coordinated acetonitrile molecule. The Ag complex is a dinuclear species with the one silver atom being 3-coordinate and the other 4-coordinate. Each of the SPBn3 molecules forms a Ag–C η1-bond with one of the aromatic rings thus blocking the coordination of further SPBn3 ligands. The two Ag centers are linked by a bridging sulfur and a weaker interaction with carbon from the aromatic ring of the same tribenzylphosphane sulfide.
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