New Soluble Polysiloxane Polymers Containing a Pendant Terdentate Aryldiamine Ligand Substituent Holding a Highly Catalytically Active Organometallic Nickel(II) Center

A new type of grafted polysiloxane polymer is described in which an aryldiamine, [CsH3(CHzNMe2)2-2,61-, provides a pendant terdentate ligand environment for catalytically active (0rgano)nickel center. The novel strategy employed involves initial of the aryl bromide 5-amino-2-bromo-1,3-bis[(dimethylamino)methyllbenzeinnet o side chain of poly((2-(chlorocarbonyl)ethyl)methylsiloxane~f ollowed by nickel incorporation an oxidative addition reaction with [Nio(COD)21 (COD = cycloocta-1,5-diene). polymers with different amounts of nickel incorporation have been prepared and by NMR, FT-IR, and W/vis spectroscopy as well as by differential scanning (DSC) and gel permeation chromatography (GPC). These polymeric materials an immobilized organonickel(I1) center show good catalytic activity in the Kharasch reaction of polyhalogenated alkanes to alkenes that is of the same order of magnitude for the comparable model organonickel(I1) complex [Ni{ CsH2(CH2NMe2)2-2,6-N(H)C(O)--4)BrI.