Structurally well-defined group 4 metal complexes as initiators for the ring-opening polymerization of lactide monomers
Polylactide (PLA) is an attractive polymeric material due to its origin from annually renewable resources and its biodegradability. The ring-opening polymerization (ROP) of lactide initiated by Lewis acidic and oxophilic metal-based catalysts constitutes the method of choice to access PLA in a contr...
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| Published in | Dalton transactions : an international journal of inorganic chemistry Vol. 42; no. 25; pp. 97 - 923 |
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| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
England
Royal Society of Chemistry
07.07.2013
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| Subjects | |
| Online Access | Get full text |
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| Summary: | Polylactide (PLA) is an attractive polymeric material due to its origin from annually renewable resources and its biodegradability. The ring-opening polymerization (ROP) of lactide initiated by Lewis acidic and oxophilic metal-based catalysts constitutes the method of choice to access PLA in a controlled and stereoselective manner. The design and synthesis of ligand-supported metal complexes to act as effective ROP initiators of lactide monomers have been the subject of numerous investigations over the past decades. In view of their oxophilic nature, well-defined group 4 metal complexes supported by polydentate supporting ligands have appeared as active initiators for lactide ROP. This perspective summarizes various classes of structurally well-defined group 4 metal initiators developed for lactide ROP. It also provides observed trends regarding their catalytic performance. Whenever appropriate and possible, catalyst structureROP performance (
i.e.
activity, control and stereoselectivity) relationships are rationalized.
Group 4 metal complexes supported by polydentate supporting ligands have appeared as a new family of active initiators for the ring-opening polymerization (ROP) of lactide monomers. This perspective summarizes the various classes of group 4 metal initiators. |
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| Bibliography: | Samuel Dagorne obtained his undergraduate degree at the University of Rennes (France) in 1994. In 1995, he joined the group of Professor Richard F. Jordan at the University of Iowa (Iowa City, USA) and graduated with a Ph.D. working on chiral zirconocenes and group 13 compounds. In 1999, he joined Professor Richard R. Schrock's group (MIT, USA) as a post-doc working on molybdenum alkylidenes. Back in France, he joined the C.N.R.S. in 2000 as an associate researcher and is currently at The Universit of Strasbourg (France). His research interests include the synthesis, reactivity and use in catalysis of oxophilic organometallics. Andreas Kapelski studied chemistry at RWTH Aachen University. He received his diploma in chemistry in 2009. From October 2009 to January 2013 he worked on his doctoral thesis, supervised by Prof. Jun Okuda at the same university. His research experiences are in the domains of organometallic chemistry and stereocontrolled polymerization of lactide monomers. Andreas Sauer studied chemistry at RWTH Aachen University and received his diploma in 2010. He was awarded a Henry Ford Scholarship for a research project in the group of Prof. Kazushi Mashima at Osaka University during his undergraduate studies in 2008. For his ongoing doctoral studies, he joined the group of Prof. Jun Okuda at RWTH Aachen University within the framework of the DFG supported International Research Training Group Selectivity in Chemo- and Biocatalysis (GermanyJapan). His research interests are bis(phenol) based group 4 metal complexes as catalysts for stereoselective polymerization. Moshe Kol received his PhD degree from Tel Aviv University in 1991 under the guidance of Prof. Shlomo Rozen working on oxidizing reagents derived from elemental fluorine. Following a two-year postdoctoral study at MIT with Prof. Richard Schrock working on dinitrogen activation, he returned to Tel Aviv University where he has been a Professor of Chemistry since 2006 and is the holder of the Bruno Landesberg Chair of Green Chemistry. His current research interests include the design of chelating ligands for early transition metals and main-group elements, and application of the resulting complexes in stereoselective synthesis, with emphasis on isoselective propylene polymerization and lactide polymerization. Jun Okuda received his Dr rer. nat. degree at the RWTH Aachen University in 1984 with G. E. Herberich and was a Postdoctoral Associate at MIT with R. R. Schrock. After his habilitation at TU Munich he held academic positions at the State University of New York at Albany, the University of Marburg, and the University of Mainz before assuming the Chair of Organometallic Chemistry at the RWTH Aachen University in 2003. His research interests include ligand design for reactive organometallics, mechanistic study of homogeneous catalysts, and polymerization catalysis. Christophe Fliedel completed his PhD under the supervision of Dr Pierre Braunstein at the University of Strasbourg (France) working on S-functionalized NHCs and DPPA-type ligands and their metal complexes. He moved in 2010 to the New University of Lisbon (Portugal) for a post-doctoral stay under the joint supervision of Prof. Teresa Avils and Dr Samuel Dagorne, focusing on the synthesis of highly Lewis acidic complexes and their use in ROP of cyclic esters. In 2011, he was awarded a post-doctoral fellowship from the Fundao para a Cincia e a Tecnologia (Portugal) to continue his research on this topic. ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 1477-9226 1477-9234 1477-9234 |
| DOI: | 10.1039/c3dt00010a |