An AmbiphilicPhosphide with Three Different CoordinationModes to Group 7–10 Metals

Phosphide anions PX₂^– with electron-withdrawing substituents display ambiphilic properties. The use of P(V) thiophosphorane substituents enables the coordination of the resulting bis(thiophosphoranyl)phosphide anion (<b>BTPP</b> = <b>L</b>) to a variety of transition metals from groups 7 to 10. A series of homoleptic and heteroleptic complexes was synthesized and X-ray diffraction analysis revealed that, depending on the metal, <b>L</b> may adopt three coordination modes (κ³-(S, P, S); κ²-(S, S); κ²-(S, P)) supporting three distinct geometries (octahedral; tetrahedral; square planar). Complex <b>L</b>_<b>2</b><b>Co</b> displays Single Molecule Magnet (SMM) properties, and complex <b>LRh(COD)</b> (COD = 1,5-cyclooctadiene) catalyzes the hydrosilylation of terminal alkynes.