Siloxane Polymers with Pendant Metal Carbonyl Groups

Abstract

The first transition metal organometallic polymer, polyvinylferrocene, was reported in 1955.¹ Since then, organometallic polymers have been extensively studied due to their potential utility in applications such as catalysts, UV stabilizers, ceramic precursors, and electrode modifiers.² While investigating the use of organometallic polymers as adhesion promoters, we found that metal carbonyl complexes with vinylcyclopentadienyl ligands could be hydrosilated with polysiloxanes containing Si-H bonds. During the course of our work, a similar hydrosilation of vinylferrocene and electrode modification with the resulting polymer was reported.³ We have found that pendant metal carbonyl groups may be used to photo-adhere polymers to substrates having basic surface groups, such as many metal oxides. This chapter details the adhesion chemistry of metal carbonyl containing polymers, the synthesis and characterization of CpMn(CO)₃ and (arene)Cr(CO)₃ containing polysiloxanes, the conversion of a-hydroxyalkylcyclopentadienyl complexes to ether byproducts during the synthesis of vinylcyclopentadienyl complexes, and an unexpected product from the hydrosilation of vinylferrocene with triphenylsilane.