1. MO Calculations of Imine Hydrolysis and Cu Complex Formation. CHM 6440/7440 Winter 2005 By Rabab Aoun

2. Outline Introduction My Project Reaction Mechanism MO Calculations and reaction energy Substituents Effect

3. Introduction Many studies on the hydrolysis of imines in the presence of, and. Alkaline hydrolysis of the imine anion involves intermolecular general base catalysis. The effect of stabilizing the aldimine linkage to hydrolytic splitting is maximum for. Generation of complexed phenoxyl-containing species depends on the presence of substituents at the ortho and para positions of the phenolate ring.

4. My Project Hydrolysis of imine in the presence of. Imine hydrolysis by triethylamine and water. Computational studies investigating all the parts of the reaction.

5. Imine Hydrolysis Reaction HBPIE t-butyl Phenol Pyridine +

6. Cu Complex Reaction 2 + 2 +

7. Mechanism of Hydrolysis

9. MO Calculations Standard ab initio molecular orbital calculations are performed at B3LYP/ 6-31G(d) Optimization and frequency method calculation Collection of electronic energy and zero point correction.

10. Energy HBPIE-1001.83691895 a.u. -76.4089533236 a.u. Reactant-1078.245872 a.u. t-butyl Phenol-735.282945673 a.u. Pyridine-342.940914839 a.u. Product-1078.223861 a.u Reaction.022011488 a.u Reaction13.8 Kcal/mol MO Calculations of Imine Hydrolysis

11. MO Calculations of Cu complex Energy -1639.21308383 a.u. 2( t-butyl Phenol)2*(-735.282945673) a.u. Reactant-3163.778975 a.u. Cu-Complex (product) (-3109.78531973 a.u.) Not Completed ReactionNot Completed

12. Cu Monomer and its Radical Cu MonomerCu Radical SCF Energy (a.u.) -3109.78531973-3109.52753697

13. t-butyl Phenol and its Radical t-butyl PhenolRadical SCF Energy (a.u.) -735.282945673-734.999198230 C-O bond length1.357571.30812

14. Substituent’s Effect on Phenoxyl Complexes The generation of complexed phenoxyl- containing species depends on the presence of substituents at the ortho and para positions of the phenolate ring. Unsubstituted phenolates are much less electroactive than those containing bulky electron-donor t-butyl groups.

15. Current Developing Studies The chemistry of electroactivity of phenoxyl species is being developed with several di- and trivalent ions in order to evaluate the geometries preferences of the ligands.

16. References 1. Anadi C. Dash, Bhaskar Dash, and Prasanna Kumar Mahapatra, J. Chem. Soc., Dalton Trans. 1983,1503. 2. Nathan E. Hall and Brian J. Smith, J. Phys. Chem., 1998, 102, 4930-4938. 3. Margaret Brault, Ralph M. Pollack, and Charles L. Bevins, J. Org. Chem., Vol. 41, No. 2,1976 4. Jack Hine, Francis A. Via, Judith K. Gotkis, and John C. Craig, Jr., Journal of the American Chemical Society,1 92:17 / August 26, 1970

17. Thanks Dr. Schlegel Dr. Hrant P. Hratchian Marco Mallard Barbara Others