Migration Insertion Polymerization (MIP) of Cyclopentadienyldicarbonyldiphenylphosphinopropyliron (FpP): A New Concept for Main Chain Metal-Containing Polymers (MCPs)

Abstract

We report a conceptually new polymerization technique termed migration insertion polymerization (MIP) for main chain metal-containing polymer (MCP) synthesis. Cyclopentadienyldicarbonyldiphenylphosphinopropyliron (FpP) is synthesized and polymerized via MIP, resulting in air stable poly(cyclopentadienylcarbonyldiphenylphosphinobutanoyliron) (PFpP) displaying narrow molecular weight distribution. The backbone of PFpP contains asymmetric iron units connected by both phosphine coordination and Fe-acyl bonds, which is representative of a new type of polymer. Furthermore, PFpP is tested to be soluble in a wide range of organic solvents and shown to possess reactive Fp end groups. PFpP amphiphiles have therefore been prepared via an end group migration insertion reaction in the presence of oligoethylene phosphine.

Synthesis and reactivity of (pyrazol-1-yl)acyl iron complexes

“…Furthermore, the metal-acyl unit has been introduced into the main chain of polymers to form potential functional organometallic materials [10,11], which develops the new application fields of metal-acyl complexes. In addition, since the successful elucidation of the structure of [Fe]-hydrogenase [12] indicated that an acyl-iron ligates to the active site of [Fe]-hydrogenase [13e15], many acyl iron complexes have been synthesized as biomimetic models for the active site of [Fe]-hydrogenase [16e25], which greatly promotes the development of metal-acyl complexes and widely broadens the potential application areas of metal-acyl complexes.…”

Synthesis and migration insertion polymerization (MIP) of CpFe(CO)2(CH2)6PPh2(FpC6P) for PFpC6P: macromolecule stability, degradability and redox activity

“…11 Unfortunately, the monomers cannot be isolated, and the resulting polymer cross-links over time, rendering it difficult to investigate the polymerization in detail. 29 FpC3P contains a functional group of CpFe(CO) 2 (Fp) with a phosphine ligand tethered via a propyl spacer. 29 FpC3P contains a functional group of CpFe(CO) 2 (Fp) with a phosphine ligand tethered via a propyl spacer.…”

“…FpC3P can undergo a migration insertion reaction (MIR) at elevated temperature (>40°C). 29 Consequently, intermolecular MIRs are promoted, leading to a new type of main chain MCP, PFpC3P. phosphine).…”

“…As a result, an acyl ligand is formed via the combination of CO and alkyl ligands, which generates one free orbital on Fe for coordination with an incoming ligand (e.g. 29 The polymer represents a new group of MCPs 1 as well as phosphorus-containing polymers. 30 In solution, intramolecular cyclizations via Fe-P coordination are major reactions, especially at low FpC3P concentration.…”

“…30 In solution, intramolecular cyclizations via Fe-P coordination are major reactions, especially at low FpC3P concentration. 29 PFpC3P is soluble in organic solvents and has sufficient stability for GPC analysis, which is particularly important in the context of MCP research, and allows us to investigate MIP in further detail. 29 Consequently, intermolecular MIRs are promoted, leading to a new type of main chain MCP, PFpC3P.…”