Related Experiment Video
Updated: Jul 15, 2026

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
Published on: December 16, 2022
Radical polymerization of styrene controlled by half-sandwich Mo(III)/Mo(IV) couples: all basic mechanisms are
E Le Grognec1, J Claverie, R Poli
1Laboratoire de Synthèse et d'Electrosynthèse Organométalliques, Faculté des Sciences Gabriel, Université de Bourgogne, 6 Boulevard Gabriel, 21000 Dijon, France.
Abstract:
Density functional calculations of bond dissociation energies (BDEs) have been used as a guide to the choice of metal system suitable for controlling styrene polymerization by either the stable free radical polymerization (SFRP) or the atom transfer radical polymerization (ATRP) mechanism. In accord with the theoretical prediction, CpMo(eta(4)-C(4)H(6))(CH(2)SiMe(3))(2), 2, is not capable of yielding SFRP of styrene. Still in accord with theoretical prediction, CpMo(eta(4)-C(4)H(6))Cl(2), 1, CpMo(PMe(3))(2)Cl(2), 3, and CpMo(dppe)Cl(2) (dppe = 1,2-bis(diphenylphosphino)ethane), 4, yield controlled styrene polymerization by the SFRP mechanism in the presence of 2,2'-azobisisobutyronitrile (AIBN). This arises from the generation of a putative Mo(IV) alkyl species from the AIBN-generated radical addition to the Mo(III) compound. The controlled nature of the polymerizations is indicated by linear M(n) progression with the conversion in all cases and moderate polydispersity indices (PDIs). Controlled polymerization of styrene is also given by compounds 3 and 4 in combination with alkyl bromides. These complexes then operate by the ATRP mechanism, again in accord with the theoretical predictions. Controlled character is revealed by linear increase of M(n) versus conversion, low PDIs, a stop-and-go experiment, and (1)H NMR and MALDI-TOF analyses of the polymer end groups. The same controlled polymerization is given by a "reverse" ATRP experiment, starting from AIBN and CpMo(PMe(3))(2)Cl(2)Br, 5. On the other hand, when compound 1 or 2 is used in combination with an alkyl bromide (as for an ATRP experiment), the isolated polystyrene shows by M(n), (1)H NMR, and MALDI-TOF analyses that catalytic chain transfer (CCT) radical polymerization takes place in this case. Kinetics simulations underscore the conditions regulating the radical polymerization mechanism and the living character of the polymerization. The complexes herein described are ineffective at controlling the polymerization of methyl methacrylate.
More Related Videos
07:14Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
04:51Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Related Concept Videos
¹H NMR: Complex Splitting
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
Radical Reactivity: Steric Effects
Along with electronic factors, steric factors also account...
Radical Substitution: Allylic Bromination
Polymer Classification: Stereospecificity
Cycloaddition Reactions: MO Requirements for Photochemical Activation