Transition-Metal-Containing Polymers by ADMET: Polymerization of cis-Mo(CO)₄(Ph₂P(CH₂)₃CH═CH₂)₂

Abstract

Polymerization of the cis-Mo(CO)4(Ph2P(CH2)3CHCH2)2 complex using acyclic diene metathesis (ADMET) polymerization is reported. Ideally, ADMET polymerization is performed in bulk monomer to maximize monomer concentration and favor formation of polymer. The monomer in this case is a solid with a melting temperature of 128 °C, which is well above room temperature and above the range of catalyst stability. The polymerization was carried out therefore in a concentrated solution of toluene. The complex underwent polymerization when catalyzed with Grubbs’ second-generation catalyst; neither Grubbs’ first-generation catalyst nor Schrock’s catalyst was active. Homopolymerization resulted in oligomers of M n = 2060 (n ≈ 3, GPC relative to polystyrene). At elevated temperatures the coordination core of the polymerized cis-Mo(CO)4(Ph2P(CH2)3CHCH2)2 complex isomerized to the trans geometry. Copolymerization with 1,9-decadiene was also carried out and resulted in an oligomer of slightly higher molecular weight, M n = 5800. It is suggested that ADMET is not an effective method for obtaining high molecular weight polymers in this case because the monomer is neither a liquid nor a low-melting solid, and therefore a high monomer concentration could not be achieved.

Synthesis of Main‐Chain Metal Carbonyl Organometallic Macromolecules (MCMCOMs)

“…Attempts to polymerize complex 4, in which C = C unit is part of the phosphine, via ADMET using different catalysts were not successful and only oligomers with a DP of ca. 3 were produced . This inability of polymerization was probably attributed to the steric effect caused by the short alkyl chain connecting metal and C = C group .…”

Vegetable oils as platform chemicals for polymer synthesis

“…It has been demonstrated that ADMET polymerization can proceed in the presence of heteroatoms, as long as the terminal olefins are far enough apart from them [40]. There are many examples of ADMET of heteroatom-containing a,v-dienes in the literature, since the introduction of functionalities in the backbone of the polymers provides different properties and permits further modifications [41][42][43].…”

Molybdenum Carbonyl Complexes with a Polymerizable Phosphorus/Nitrogen/Phosphorus Ligand and Corresponding Conducting Metallopolymers

“…Schrock and coworkers synthesized polymer‐supported chiral Mo‐based complexes as efficient catalysts for enantioselective olefin metathesis . Shultz and coworkers reported the acyclic diene metathesis (ADMET) polymerization of an organometallic molybdenum‐containing diene ( cis ‐Mo(CO) 4 (Ph 2 P(CH 2 ) 3 CHCH 2 ) 2 ) and its copolymerization with an organic diene ( Figure ) . Kim et al.…”

“…This wide Molybdenum-containing hybrid and coordination polymers have been reported for a variety of applications. [40][41][42][43][44][45][46][47][48][49] For example, Boruah et al have reported polymer anchored peroxo compounds of vanadium(V) and molybdenum(VI) for their activities with alkaline phosphatase (ALP) and catalase. [40] In another example, Moreno et al have prepared (hydroxypropyl)-2-aminomethyl pyridine containing hybrid polymer-silica SBA-15 materials supporting Mo(VI) centers and they studied it for heterogeneous catalysts for oct-1-ene epoxidation.…”

“…[43] Shultz and coworkers reported the acyclic diene metathesis (ADMET) polymerization of an organometallic molybdenum-containing diene (cis-Mo(CO) 4 (Ph 2 P(CH 2 ) 3 CHCH 2 ) 2 ) and its copoly merization with an organic diene (Figure 1). [44] Kim et al synthesized terthiophene-bearing pendant organomolybdenum complexes and electropolymerized them to obtain electroactive films. [37,50] The purpose of this study was to synthesize and characterize an electropolymerizable tridentate ligand and then corresponding molybdenum complexes with carbonyl groups, and electropolymerization of these compounds.…”