Siloxane Polymers with Pendant Metal Carbonyl Groups
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.
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