This journal is c The Royal Society of Chemistry 2010 Chem. Commun., 2010, 46, 7879–7893 7879 Designing late-transition metal catalysts for olefin insertion polymerization and copolymerization Drexel H. Camacho a and Zhibin Guan* b Received 22nd May 2010, Accepted 12th August 2010 DOI: 10.1039/c0cc01535k The innovation of polyolefin with unique architecture, composition and topology continues to inspire polymer chemists. An exciting recent direction in the polyolefin field is the design of new catalysts based on late-transition metals. In this review, we highlight recent developments in rationally designing late-transition metal catalysts for olefin polymerization. The examples described in this review showcase the power of the design of well-defined late-metal catalysts for tailored polyolefin synthesis, which may usher in a new era in the polymer industry. 1. Introduction Polymeric materials, including plastics, fibers, and elastomers, play an essential role in our life. Polyolefins are an important family of polymers, with billions of pounds produced annually. 1 Given the abundance and low cost of olefinic monomers from the petroleum industry, it is particularly attractive to develop efficient polymerizations to transform these simple monomers into novel polymeric materials. The range of polyolefin products will grow steadily to meet the increasingly sophisticated needs of consumers. 2 The industry therefore requires constant innovation of novel polymer structures for new applications. To meet this goal, it is essential to continuously discover and develop new polymerization chemistry. This industrial imperative is aptly echoed in the general roadmap proposed by the Council of Chemical Research for achieving what is referred to as the Vision 2020 Catalysis 3 goals. The ‘‘identification of methods for achieving control of polymer architecture and composition’’ is one of the targets in the area of polymerization. This goal calls for a ‘‘new catalyst design through combined experimental, mechanistic understanding, and improved computational modeling of catalytic processes’’ for the advancement of polymerization chemistry. An exciting research effort in this direction is the design and development of new catalytic systems that efficiently convert common olefin feedstock into high value polymeric materials. 4 Historically, the design of new catalysts for olefin polymerization has mostly focused on early transition metals. 5 Recently, however, there has been a renaissance in the development of late-transition metal-based systems. 6 In the last decade, a variety of well-defined late-transition metal complexes with specific catalytic properties have been designed to afford polymers with unique architectures. 7 Through highlighting recent examples from others’ and our own laboratory, this article briefly reviews the evolution in designing late-transition metal catalysts for insertion polymerization and a Chemistry Department, De La Salle University – Manila, 2401 Taft Avenue, Manila, 1004 Philippines. E-mail: drexel.camacho@dlsu.edu.ph; Fax: +63 2 5360230; Tel: +63 2 5244611 Loc 430 b Department of Chemistry, University of California, 1102 Natural Sciences 2, Irvine, CA, 92697-2025, USA. E-mail: zguan@uci.edu; Fax: +1 9498242210; Tel: +1 9498245172 Drexel H. Camacho Drexel H. Camacho was born in Maguindanao, Philippines, in 1972. After finishing his BS at Philippine Normal Univer- sity, and MSc at De La Salle University-Manila, he went to Tohoku University, Japan for his PhD degree (2002) under Prof. Yoshinori Yamamoto. Following a postdoctoral stint at the University of California-Irvine with Prof. Zhibin Guan, and an R&D job in the semiconductor industry, he joined the chemistry faculty with De La Salle University-Manila in 2009 as an associate professor. He was awarded the TWAS Prize, the NAST Outstanding Young Scientist, and the NRCP Research Award. His research interests include organometallics and polymers. Zhibin Guan Zhibin Guan is a professor of Chemistry at the University of California, Irvine. He obtained BS and MS degrees at Peking University, and PhD degree at UNC-Chapel Hill. Following a postdoctoral stint at Caltech, he spent five years at DuPont before moving to academic in 2000. He has received numerous awards, including the Beckman Young Investigator Award, the NSF CAREER award, the Camille Dreyfus Teacher- Scholar Award, and the Humboldt Bessel Award. He was elected as a Fellow of the American Association for Advancement of Science. His research interests span the broadly defined fields of organic, biological, and macromolecular materials chemistry. FEATURE ARTICLE www.rsc.org/chemcomm | ChemComm