Quaternary onium chlorometallates as hydrosilylation catalysts

Sixteen triethylbenzylammonium chlorometallates [Et 3 NCH 2 Ph]   m + [MCI n ] m − (M= transition metal, m = 1–3, n = 3–6) and nine anchored ionic metal complexes [℗–CH 2 PBu 3 ]   m + [MCI n ] m − derived from ‘polymer‐bound tributylmethylphosphonium chloride’ have been prepared. All the complexes were studied as catalysts in the hydrosilylation of phenylacetylene with triethylsilane. The homogeneous Rh III , Pt IV , Ir III , Cu II , Zn II , Fe III and anchored Pt IV , Rh III , Os IV complexes were found to be active in this reaction. The regio‐ and stereoselectivity of the following catalyst types is determined by the metal atom involved, being a weak function of the chemical environment; neutral chloride (MCl n–m ); acid (H 2 MCl 6 ); salt containing the lipophilic organic cation ([Et 3 NCH 2 Ph]   m + [MCl n ] m − ); polymer‐supported metallate anion ([℗–CH 2 PBu 3 ]   m +[MCl n ] m − ).