1. Temperature Controlled Rate Studies of Co(salen) Reversible Oxygen Binding
By Philip Chuang

2. Background Information
Co(salen) is Cobalt N,N’-bis (salicylaldehyde) ethylenediamine
Ability to reversibly bind oxygen discovered by Tsumaki in 19381
A square planar dioxygen carrier
Exists in both an Active and Inactive state
Interested in Effect of Temperaturee on Rate in:
Oxygenation of Inactive Co(Salen) in DMSO
[(DMSO)Co(Salen)]2 + O2  [(DMSO)Co(Salen)]2O2
Deoxygenation of Active Co(salen) in CHCl3
Co(Salen)O2  Co(Salen) + O2

3. Active State vs. Inactive State
Active State binds Oxygen readily
Dimeric Form coordinates between Cobalt centers.2
Binds Oxygen in polar aprotic solvents
Dimeric Form coordinates Co and O.3
Diagram from Reference 2
Diagram from Reference 3

4. Hypothesis
The Rate of Oxygen Binding and Dissociation increases with Higher Temp. More specifically:
The Rate of Inactive Co(salen) Oxygenation will Increase with Temperature in DMSO.
Rate of Active Co(salen) Deoxygenation will Increase with Temperature in chloroform.

5. Synthetic Method Synthesis of Inactive Co(salen)
1 eq. ethylenediamine added to 2 eq. Salicylaldehyde in boiling ethanol, for 4 min.
1 eq. Salen product (from above) refluxed in ethanol under Argon, 1 eq. Cobalt Acetate in H2O added via addition funnel
Stirred and kept in 700C Water bath for 1 hour
Synthesis of Active Co(salen)
Same methods as Inactive, but no hot water bath
Procedure derived from Reference 4

6. UV-Vis
UV-VIS of Inactive Co(salen) in DMSO in atmosphere
UV-Vis of Inactive Co(salen) in DMSO in N2 from literature5
The UV spectra indicates that the Inactive product was obtained.
Differences between UV spectra likely due to availability of Oxygen in the DMSO solution

7. H-NMR -The H-NMRs did not correspond to predicted H-NMRs
H-NMR of Active Product in dDMSO
H-NMR of Inactive Product in dDMSO
-The H-NMRs did not correspond to predicted H-NMRs
-Conclusive Identification from H-NMR unobtainable
-Future improvement: prepare H-NMR in inert atmosphere, include C13 NMR

8. IR Spectra
IR Spectra of inactive Co(salen) from Unniversity of Wimona6
IR spectra of Inactive Co(salen)
With the exception of the C-H peak at 3000, and the nujol peaks at 1500, 1400 and 700 cm-1 look similar
Further reinforces likelihood of obtaining Inactive Product

9. UV-Vis Kinetics Results pt.1
Absorbance vs Time graph of oxygenated Co(salen) in CHCl3 at 150C
Absorbance vs. Time graph of oxygenated Co(salen in CHCl3 at 150C, excluding first 8 data points
The first 8 data points were removed
Not enough time given to allow temperature to equilibrate

10. UV-Vis Kinetics Results pt. 2
Absorbance vs. Time graph of oxygenated Co(salen) in CHCl3 at 500C
Absorbance vs. Time graph of oxygenated Co(salen) in CHCl3 at 500C without first 8 data points
Again, the first 8 data points were discarded.
Not enough time was given for temperature to equilibrate

11. UV-Vis Spectra Results pt. 3
-LN Absorbance vs Time plot for 150C deoxygenation of Inactive Co(salen)
-LN Absorbance vs. Time plot for 500C deoxygenation of Inactive Co(salen)
The slope of the –LN Absorbance vs. Time plot yields the rate constant of a first order reaction.

12. UV-Vis Kinetics Results pt. 4
Absorbance vs. Time plot for Inactive Co(salen) in DMSO at 150C
-LN Absorbance vs. Time plot for Inactive Co(salen) in DMSO at 150C
No Data points were removed
For the DMSO runs, temperature was allowed to equilibrate

13. UV-Vis Kinetics Results pt. 5
Absorbance vs. Time graph of inactive Co(salen) in DMSO at 500C
Result was not workable, rate could not be calculated
Possible explanations in Discussion Section

14. Discussion
When LN Absorbance vs. LN Time plotted (not pictured), linearity observed
Indicated a first order reaction:
R = k[A]  -d[A]/dt = k[A]
-d[A]/[A] = k Integrate to get LN [A] = -kt
Thus k = -LN [A] /t
This method used to attain reaction rates from results
Decreasing absorbance indicative of oxygen complex formation5

15. Discussion
k = /s for oxygenated Active Co(salen) in CHCl3 at 150C in atmospheric conditions
Validity in question due to low correlation coefficient
k = /s for oxygenated Active Co(salen) in CHCl3 at 150C in atmospheric conditions
k = /s for inactive Co(salen) in DMSO at 150C
k could not be determined for inactive Co(salen) in DMSO at 500C
Possible Reason: Reaction has finished
Supported by the lower absorbance compared to the 150C sample.

16. Conclusions
Data supports hypothesis for increased rate of Oxygen Dissociation for Oxygenated Co Active Co(salen) at increased temperatures
Not enough data to support or disprove hypothesis for increased rate of Oxygen uptake in Active form of Co(salen at increased temperatures.
Future Considerations:
Prepare NMRs and UV-Vis solutions in an inert glovebox using a sealable cuvette
Take the C13 NMR to better characterize products
Run more samples at different temperatures to give better overall picture

17. References T. Tsumaki, Bull. Chem. Soc. Jpn., 13, 252 (1938).
Schaefer, W. P., and Marsh, R. E., Acta Crystallogr., B25, 1675 (1969)
Bruckner, S.,Calligaris, M., Nardin, G., and Randaccio, L., Acta Crystallogr., B25, 167 (1969)
Bailes, R. H., and Calvin, M., J. Amer. Chem. Soc., 69, 1886 (1947)
B. Ortiz, and Park, S., Bull. Korean Chem. Soc. 21, 4, (2000)

18. Acknowledgements
I’d like to thank Ankur for always being available to help me at all hours of the day
Simone for being a big help during the lab sessions and being ridiculously funny
Professor Roth for allowing me to use her temperature controlled UV-Vis and giving us a cool, albeit hard final project that taught us to make use of the journal articles available to us
Finally my fellow students for being ever supportive and cheery