Catalysis in Acyclic Diene Metathesis ADMET Polymerization

Catalysis in Acyclic Diene Metathesis (ADMET) Polymerization 

Olefin metathesis (OM) has proven to be one of the most important advances in catalysis in recent years based on the application of this chemistry to the synthesis of polymers and biologically relevant molecules [1-10]. This unique transformation promotes chain and condensation polymerizations, namely ring opening metathesis polymerization and acyclic diene metathesis polymerization (ADMET). Applications of metathesis polymerization span many aspects of materials synthesis from cell-adhesion materials [11] to the synthesis of linear polyethylene with precisely spaced branches [12]. 

This chapter will present some of the history of ADMET and olefin metathesis in general, although the emphasis will be on the mechanism and kinetics of ADMET polymerization. The general mechanism for olefin metathesis will be presented before any of the specific catalyst structures are introduced or discussed in order to provide the reader with a firm basis upon which to compare the various popularly used catalysts for ADMET polymerization. In addition, procedural information will be given at the end of the chapter to give the reader an idea of what is specifically involved in a typical ADMET polymerization. 

This chemistry is always metal-catalyzed, and is presumed to proceed by a [2 -I- 2] cycloaddition of a metal carbene with an olefin to produce a metaUacyclobu- 

Edited by Bernhard Rieger, Lisa Saunders Baugh, Sinita Kacker, Susanne Striegler Copyright 200.. WILEY-VCH Verlag GmbH Co. KGaA, Weinheim ISBN 3-527-30455-5 

---

Lehman, S. E., Jr., Wagener, K. B. Catalysis in acyclic diene metathesis (ADMET) polymerization. (Late Transition Metal Polymerization Catalysis). 2003, 193-229... 

In the field of alkene metathesis ruthenium-allenylidene precursors have made, since 1998, an important contribution to catalysis [12, 31, 32], for the formation of cycles and macrocycles via RCM, ROMP and acyclic diene metathesis (ADMET) polymerization. 

---