Telomerization of Isoprene with Short Alcohols Using Novel Solid Molecular Phosphine Polymers

ABSTRACT Palladium‐loaded phosphine polymers have been designed and used as solid molecular catalysts (SMCs) in telomerization reactions with isoprene and short alcohols. A novel tris‐(2‐methoxyphenyl)phosphine‐based polymer (pTOMPP), previously reported poly triphenylphosphine (pTPP) as well as TPP‐based polymers with trigonal and tetragonal linkers were tested either pre‐loaded or in‐situ‐loaded. The novel polymer pTOMPP proved to be an excellent support material during in‐situ‐loading, outperforming triphenylphosphine based polymers. Surprisingly pre‐loaded SMCs resulted in significantly lower activity. XAS studies reveal that the enhanced activity of Pd/pTOMPP is due to the coordination sphere of Pd on the polymer showing a higher contribution of Pd‐P bonds forming, whereas XAS spectra of Pd/pTPP show a higher contribution of inactive Pd‐acac bonds. Especially pre‐loaded polymers show little Pd‐P interactions.