A Phosphine-Based Heterotrimetallic (M = Fe, Ru, W) Homopolymer

Abstract

An organometallic homopolymer containing three different metals per repeating unit was synthesized from an air-and moisture-stable secondary phosphine bearing ethylferrocene and ethylruthenocene groups. Hydrophosphination yielded a tertiary phosphine bearing an alcohol, which was then used to introduce a polymerizable styrene group via DCC coupling. Freeradical polymerization, followed by post-polymerization coordination to photogenerated W(CO) 5 units yielded the title polymer, which showed thermal, spectroscopic, and electrochemical properties associated with each of the transition metals involved. Scheme 1. Synthesis of heterometallic polymers 4, 4•S, and 4•W(CO) 5. Rc = ruthenocene, Fc = ferrocene.

Polymer networks functionalized with low‐valent phosphorus cations

“…[ 1,2 ] For example, functionalizing the non‐bonding pair of electrons on trivalent phosphorus centers has been adopted by polymer chemists taking the lead from small molecule systems to tune electrochemical and optical properties. [ 3–12 ] Meanwhile, examples where post‐polymerization functionalization of trivalent phosphorus‐containing polymers leads to advantages that are unique to macromolecular over molecular systems include polymers that can scavenge homogenous catalysts [ 13,14 ] and an ability to tune the shapes and sizes of self‐assembled nanostructures. [ 15 ] There remains a slew of sophisticated p block reactions that take place with molecular phosphines, which have yet to be translated to a macromolecular context, [ 16 ] leaving an area of untapped potential in material exploration and development.…”

Metallized Phosphane–Ene Polymer Networks as Precursors for Ceramics with Excellent Shape Retention

“…All that is required for postpolymerization functionalization is a mechanism of binding these molecular precursors to the polymer scaffold. Coordination chemistry and ion exchange are the mechanisms that have been explored the most. ,,,,− …”