Electrostatic Potential of 3A5AF & Frontier Molecular Orbitals

HOMO

LUMO

Red area: electron rich, Blue area: electron poor

Chris Kozak* (ckozak@mun.ca), Fran Kerton* (fkerton@mun.ca) Department of Chemistry, Memorial University of Newfoundland, St.

John’s, NL, A1B 3X7 http://www.greenchemistrynewfoundland.ca

The Centre for Green Chemistry and Catalysis at Memorial University performs research in the following areas related to sustainability: (1)  Preparation of CO2-derived and biodegradable materials (2)  Use of renewable feedstocks (3)  Development of new catalysts and catalytic methods

EurJIC

EJICFK (35) 5331–5454 (2011) · ISSN 1434-1948 · No. 35/2011

[35] Eur. J. Inorg. Chem

. 2011, 5331–5454

European Journal ofInorganic Chemistry

35/20112nd December Issue

D 3715

www.eurjic.org

Cover PictureFrancesca M. Kerton et al.Zinc Complexes of Aminephenolate Ligands A Journal of

Preparation of CO2-derived materials We have been exploring the copolymerization of carbon dioxide with epoxides to yield polycarbonates. New catalysts based on either chromium or aluminum have been developed.1-3,5 Studies are ongoing to optimize ligand design and access new materials (e.g. terpolymers, telechelic polymers) with useful properties. Cobalt catalysts for the formation of cyclic carbonates have also been discovered.4

[1] R. K. Dean, K. Devaine-Pressing, L. N. Dawe and C. M. Kozak, Dalton Trans., 2013, DOI: 10.1039/C2DT31942J. [2] R. K. Dean, L. N. Dawe and C. M. Kozak, Inorg. Chem., 2012, 51, 9095−9103. [3] N. Ikpo, S. Barbon, M. Drover, L. N. Dawe and F. M. Kerton, Organometallics, 2012, 31, 8145-8158 [4] L. N. Saunders, N. Ikpo, C. F. Petten, U. K. Das, L. N. Dawe, C. M. Kozak* and F. M. Kerton*, Catal. Commun., 2012, 18, 165-7 [5] N. Ikpo, J. C. Flogeras and F. M. Kerton*, Dalton Trans., 2013, In press DOI:10.1039/C3DT00049D

Preparation of biodegradable polymers Coordination compounds of group 1 metals, zinc and aluminum have been studied for ring-opening polymerization of cyclic esters (lactide and caprolactone) to give biodegradable polyesters.6-8 The complexes show reactivity comparable with other catalyst systems and are easily prepared. Studies are ongoing to obtain kinetic data on the reaction process and thermal characteristics of the resulting polymers. [6] R. K. Dean, A. M. Reckling, H. Chen, L. N. Dawe, C. M. Schneider and C. M. Kozak, Dalton Trans., 2013, DOI:10.1039/C2DT32682E. [7] N. Ikpo, C. Hoffmann, L. N. Dawe and F. M. Kerton, Dalton Trans., 2012, 6651 – 6660. [8] N. Ikpo, L. N. Saunders, J. L. Walsh, J. M. B. Smith, L. N. Dawe and F. M. Kerton, Eur. J. Inorg. Chem., 2011, 5347-5359.

Use of renewable feedstocks The transformation of aminocarbohydrates (chitin, chitosan and N-acetylglucosamine) into renewable chemicals has been investigated,9-12 and the reactivity of the resulting molecules is currently being studied further. For example, we now have a method for preparing our amidofuran (3A5AF) in water and have also been able to prepare the amine derivative. We hope to convert these molecules into (i) monomers for polymer synthesis and (ii) bio-active compounds. Furthermore, we have also been studying the physical chemistry of 3A5AF experimentally and computationally. It is surprisingly acidic and is moderately soluble in methanol-modified carbon dioxide. A related compound 5-hydroxymethylfurfural is more soluble and does not need a co-solvent in order to dissolve in CO2.13 We are also interested in studying the chemistry of other renewable feedstocks incl. other carbohydrates, polyols, lignin and amino acids. [9] K. W. Omari, L. Dodot and F. M. Kerton, ChemSusChem, 2012, 5, 1767-1772. [10] M. W. Drover, K. W. Omari, J. N. Murphy and F. M. Kerton, RSC Adv., 2012, 2, 4642-4643. [11] K. W. Omari, J. E. Besaw and F. M. Kerton, Green Chem., 2012, 14, 1480-1487. [12] F. M. Kerton, Y. Liu, K. W. Omari and K. Hawboldt, Green Chem., 2013, 15, 860-871 [13] S. M. Payne and F. M. Kerton, Green Chem., 2010, 12, 1648 – 1653

Funding acknowledged from:

Green Chemistry Research at Memorial University

New catalysts and catalytic methods Catalytic C-C,14 C-N16 and C-O18 bond forming reactions and catalytic oxidation reactions of alkenes,15 alcohols17 and amines16 are being investigated. Reactions employ inexpensive, non-toxic metals, additives, and oxidants (air or hydrogen peroxide). [14] X. Qian, L. N. Dawe and C. M. Kozak, Dalton Trans., 2011, 40, 933-943 [15] K. Hasan, N. Brown and C. M. Kozak, Green Chem. 2011. 13, 1230-1237 [16] Z. Hu and F. M. Kerton, Org. Biomol. Chem., 2012, 10, 1618-1624 [17] Z. Hu and F. M. Kerton, Appl. Catal. A:General, 2012, 413-4, 332-339 [18] H. A. Kalviri and F. M.Kerton, Adv. Synth. Catal., 2011, 353, 3178-3186

Instruments and expertise in the Green Chemistry and Catalysis Group: Numerous instruments including GC-MS, GPC (aqueous and organic phase with triple detector), glove boxes, microwave reactors, in-situ FTIR, UV-vis-NIR, high pressure equipment incl. view cell, mixer mill, ultrasound reactor, and automated flash chromatography. Other instruments (NMR, LC-MS, ICP-MS, MALDI-ToF MS, XRD, SEM) are available within the University. As indicated above, our group has extensive experience in green polymer chemistry, small molecule activation, catalysis, alternative solvents (e.g. ionic liquids) and transformations of renewable feedstocks.

3A5AF  

PPC  

Product Metal and/or Organocatalyst Air or H2O2

Solvent-free Ionic Liquid or Aqueous

Substrate