MO Calculations of Imine Hydrolysis and Cu Complex Formation.

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.

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My Project

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

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Imine Hydrolysis Reaction

Pyridine
t-butyl Phenol
HBPIE
6
Cu Complex Reaction
Cu Complex Reaction
2

2

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Mechanism of Hydrolysis
8
Mechanism of Hydrolysis
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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.

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MO Calculations of Imine Hydrolysis
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
Reaction 13.8 Kcal/mol
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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
Reaction Not Completed
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Cu Monomer and its Radical
Cu Monomer Cu Radical
SCF Energy (a.u.) -3109.78531973 -3109.52753697
13
t-butyl Phenol and its Radical
t-butyl Phenol Radical
SCF Energy (a.u.) -735.282945673 -734.999198230
C-O bond length 1.35757 1.30812
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Substituents 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.

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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.

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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 9217 / August 26, 1970

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Thanks

• Dr. Schlegel
• Dr. Hrant P. Hratchian
• Marco Mallard
• Barbara
• Others