J. Oscar C. Jimenez-Halla 准教授

講演会 日時 12 April (Thur) 4:20 ~5:50 pm

会場������ E211 ���

演題RingOpeningPolymerizationOfTheL-LactideUsingBismuth

CompoundsAsCatalysts : AComputational&Experimentalstudy

Dr. J. Oscar C. Jimenez-Halla was born in Oaxaca City in the southern state of Oaxaca, Mexico. He obtained his B.Sc. in Chemical Engineering (1st Class Hons) degree from Oaxaca Institute of Technology in 2002. Then, he received his M.Sc. degree from University of Guanajuato in 2005 and, supported by a Ph.D. scholarship, he did his PhD studies at the Institute of Computational Chemistry and Catalysis (IQCC) of University of Girona, Spain, with Profs. Dr. Miquel Solà and Dr. Juvencio Robles working on reaction mechanisms and aromaticity of small inorganic clusters. During his PhD studies, he did research stays in the groups of Prof. Dr. Thomas Cundari (North Texas University, USA) and Prof. Dr. Gernot Frenking (Marburg University, Germany). From 2010 to 2012 he has been a postdoctoral research fellow in the groups of Prof. Dr. Gabriel Merino (CINVESTAV, Merida), Prof. Dr. Fahmi Himo (Stockholm University, Sweden) and Prof. Dr. Holger Braunschweig (Julius-Maximilians Würzburg University, Germany) working on different reaction mechanisms of catalytic systems of organic and inorganic / organometallic reactions. Then, he joined the Department of Chemistry in 2013 as associate professor. He is the leader of the research group “Private Investigator Agency of Molecules”. He’s member of the Mexican Academy of Sciences, recognized for the second level (of three) of Mexican researcher system and Review Editor of Frontiers in Chemistry and Applied Science and Innovative Research journals.

Contact: 広島大学 大学院理学研究科 化学専攻 Dr. Rong Shang (assit. Prof.)

Email: rshang@hiroshima-u.ac.jp 電話番号：7429

RING OPENING POLIMERIZATION OF THE L-LACTIDE USING BISMUTH COMPOUNDS AS CATALYSTS

Lupita Ortiz-Aldaco, Gerardo Gonzalez-Garcia, Jose E. Baez,* J. Oscar C. Jimenez-Halla*

Department of Chemistry, Division of Natural and Exact Sciences, University of Guanajuato, campus Gto, Noria Alta s/n 36050, Guanajuato, Mexico.

E-mail: jebaez@hotmail.com, jjimenez@ugto.mx

We have carried out a joint computational and experimental study for the coordination-insertion ring opening polymerization of L-lactide[1

−2] using bismuth citrate, subsalicylate and

acetate.[3] Our initiator was 1-octanol and the reaction completed at 170 °C. Our DFT calculations were done at the SMD[D3-PBE0/LANL2DZpd,6-31G(d)] level for investigating the reaction mechanism in the initiation stage with the aim of predicting the activity of these catalysts. The experimental and computational results showed that the bismuth acetate is the most active catalyst in the presence or absence of initiator. Computationally, the lowest energy barrier[4] was obtained and, experimentally, high conversions and molecular weights (Mn) were obtained. For the case of the bismuth subsalicylate, it is the second more active catalyst, but it yielded a larger conversion and high molecular weights when using without the alcohol. The bismuth citrate is poorly active with or without alcohol to polymerize the L-lactide. Likewise, we obtained the expected results at the laboratory not only confirming the computational studies but complementing them.

References.

1. J. E. Baez, A. Marcos-Fernandez, J. Polym. Res. 2011, 18, 1137−1146. 2. J. E. Baez, P. Galindo-Iranzo, A. Marcos-Fernandez, Int. J. Polym. Anal. Charact., 2016, 2, 149−155. 3. L. Ortiz−Aldaco, G. Gonzalez−Garcia, J. E. Baez, J. O. C. Jimenez−Halla, Macromolecules 2018,

accepted. 4. C. Amatore, A. Jutand, J. Organomet. Chem. 1999, 576, 254−278.

Research Projects: Ionization and Activation of Metallic Cations for Systems of Biochemical Interest. Theoretical Studies and Mass Spectroscopy Research. Institut de Química Computacional, University of Girona, Spain. From January 2005 to June 2006. Head of project: Prof. Dr. Miquel Solà i Puig Air Force Laboratory Latin American Initiative Project. Department of Chemistry, University of Guanajuato, Mexico. From January to June 2010. Head of project: Prof. Dr. Gabriel Merino Characterization of Boron Containing Complexes using Density Functional Theory (Deutsche Forschungsgemeinschaft) Institut für Anorganische Chemie, Universität Würzburg. From July 2011 to June 2012. Head of project: Prof. Dr. Holger Braunschweig Theoretical Study of Electronic Structure of closo-carboranes and Reactivity of 1,2-dehydro-o- carboranes. Subsecretaría de Educación Superior, PROMEP-SEP. From September 2013 to August 2014. Head of project: Prof. Dr. J. Oscar C. Jimenez Halla Funding amount: $300,000 Mexican Peso Reactivity of [IrTpMs’’(N2)] towards [AlClXR] Compounds: In the Search of Species containing Ir-Al bonds. DAIP-UGTO. From January to December 2014. Head of project: Prof. Dr. J. Oscar C. Jimenez Halla Funding amount: $100,000 Mexican Peso Theoretical Study of Pericyclic Reactions between Fischer-type Carbenes and Iminoboranes. CONACyT – FONDO CIENCIA BASICA. From May 2015 to April 2018. Head of project: Prof. Dr. J. Oscar C. Jimenez Halla Funding amount: $2,000,000 Mexican Peso Arylation of the Vinyl Csp2-H Bond Mediated by Bisaryliodinium(III) Salts. The Mizoroki-Heck Reaction without Metals.DAIP-UGTO. From January 2016 to December 2017. Head of project: Prof. Dr. J. Oscar C. Jimenez Halla Funding amount: $200,000 Mexican Peso