numerous polyethylene or polypropylene compounds have been synthesized by metal-catalyzed coordination-insertion polymerization. On the other hand, organometallic catalysts * To whom correspondence should be addressed. E-mail: nozaki@chembio.t.utokyo.ac.jp. Akifumi Nakamura (left) was born in 1984 in Kanagawa, Japan. He received his B.S. degree in 2007 and M.S. degree in 2009 from the University of Tokyo under the guidance of Professor Kyoko Nozaki. During that time he joined Professor Keiji Morokuma’s group at Kyoto University as a visiting student. In 2009, he started his Ph.D. study at the University of Tokyo under the guidance of Professor Kyoko Nozaki. He is also a research fellow of the Japan Society for the Promotion of Science. His research interests include synthetic organic chemistry, organometallic chemistry, computational chemistry, and polymer chemistry.

Coordination−Insertion Copolymerization of Fundamental Polar Monomers

Alternating copolymerization of carbon monoxide and olefins by single-site metal catalysis

Vinyl acetate (VA) and vinyl trifluoroacetate (VAf) react with [(N∧N)Pd(Me)(L)][X] (M = Pd, Ni, (N∧N) = N,N‘-1,2-acenaphthylenediylidene bis(2,6-dimethyl aniline), Arf = 3,5-trifluoromethyl phenyl, L = ArfCN, Et2O; X = B(Arf)4-, SbF6-) to form π-adducts 3 and 5 at −40 °C. Binding affinities relative to ethylene have been determined. Migratory insertion occurs in a 2,1 fashion (ΔG⧧ = 19.4 kcal/mol, 0 °C for VA, and 17.4 kcal/mol, −40 °C for VAf) to yield five-membered chelate complexes [(N∧N)Pd(κ2-CH(Et)(OC(O)CH3))]+, 4, and [(N∧N)Pd(κ2-CH(Et)(OC(O)CF3))]+, 6. When VA is added to [(N∧N)Ni(CH3)]+, an equilibrium mixture of an η2 olefin complex, 8c, and a κ-oxygen complex, 8o, results. Insertion occurs from the η2 olefin complex, 8c (ΔG⧧ = 15.5 kcal/mol, −51 °C), in both a 2,1 and a 1,2 fashion to generate a mixture of five- and six-membered chelates, 92,1 and 91,2. VAf inserts into the Ni−CH3 bond (−80 °C) to form a five-membered chelate with no detectable intermediate. Thermolysis of the Pd chelates result...

Reactions of vinyl acetate and vinyl trifluoroacetate with cationic diimine Pd(II) and Ni(II) alkyl complexes: identification of problems connected with copolymerizations of these monomers with ethylene.

Synthesis of New Phosphine Imine Ligands and Their Effects on the Thermal Stability of Late-Transition-Metal Olefin Polymerization Catalysts

Since the prediction of the existence of metallabenzenes in 1979, metallaaromatic chemistry has developed rapidly, due to its importance in both experimental and theoretical fields. Now six major types of metallaromatic compounds, metallabenzenes, metallabenzynes, heterometallaaromatics, dianion metalloles, metallapentalenes and metallapentalynes (also termed carbolongs), and spiro metalloles, have been reported and extensively studied. Their parent organic analogues may be aromatic, non-aromatic, or even anti-aromatic. These unique systems not only enrich the large family of aromatics, but they also broaden our understanding and extend the concept of aromaticity. This review provides a comprehensive overview of metallaaromatic chemistry. We have focused on not only the six major classes of metallaaromatics, including the main-group-metal-based metallaaromatics, but also other types, such as metallacyclobutadienes and metallacyclopropenes. The structures, synthetic methods, and reactivities are described, their applications are covered, and the challenges and future prospects of the area are discussed. The criteria commonly used to judge the aromaticity of metallaaromatics are presented.

Metallaaromatic Chemistry: History and Development.

New Imine−Phosphine Palladium Complexes Catalyze Copolymerization of CO−Ethylene and CO−Norbornylene and Provide Well-Characterized Stepwise Insertion Intermediates of Various Unsaturated Substrates

and Jwu-Ting Chen

Papers

New Imine−Phosphine Palladium Complexes Catalyze Copolymerization of CO−Ethylene and CO−Norbornylene and Provide Well-Characterized Stepwise Insertion Intermediates of Various Unsaturated Substrates

Study of Insertion of Olefins and/or Carbon Monoxide into Phosphine−Imine Palladium Methyl Complexes