Synthesis and Kinetic Study of Co(Salen): A Biomimetic O2 Carrier

Abstract

Structure of Co(salen)

Co(salen) is a versatile molecule that can take different forms, such as active and inactive. Like proteins in our blood, Co(salen) is capable of reversible dioxygen uptake in either 1:1 or 2:1 ratio, depending on the solvent employed. In DMSO, it is in a 2:1 ratio, with one molecule of Co(salen) attached to each oxygen in O2, forming a sandwich complex of sorts. Co(salen) changes in color when exposed to air as does our blood. The simple structure of Co(salen) allows for studies to easily be done, and serves as a model to study the ways that oxygen carrying proteins work. This sequence describes the synthesis: 2 Co(OAc)2 + 2 SalenH2 [Co(salen)]2 + 4 HOAc INTRODUCTION Dioxygen (O2) is essential to life on earth, carried by various proteins which can reversibly bind dioxygen for the purpose of transport within the body. The proteins have a transition metal within them; iron or copper, and can reversibly bind dioxygen by a redox like process. A simple complex formed from cobalt, ethylenediamine, and salicylaldehyde can reversibly bind dioxygen as well, known as Co(salen). This small complex works in the same way as proteins do, yet is much simpler and easy to study than proteins, thus providing a model used to study the way proteins work in our body. RESULTS AND DISCUSSION The synthesis of Co(salen) started with the synthesis of 2,2'-[1,2ethanediylbis(nitrilomethylidyne)]bisphenol, commonly referred to as salen(or salenH2). Salen was formed by a condensation reaction between two molecules of salicylaldehyde and one of ethylenediamine, hence the name salen. Salen is a tetradentate chelating agent, and holds the cobalt atoms in place during the synthesis of Co(salen), which is itself a tetradentate ligand.

Figure 1. Structure of a tetradentate chelating agent, Salen.

The reaction followed the sequence: 2 Co(OAc)2 + 2 SalenH2 [Co(salen)]2 + 4 HOAc The cobalt in Co(salen) is square planar, having a d7 electron configuration, and typically makes 5 coordinate adducts.1 The Co(salen) started as a brown gelatinous precipitate, and upon refluxing turned to a bright red similar to bricks. Upon exposure to air the Co(salen) turns a dark color again, which is similar to our blood, which changes colors from a blue purple to red when it encounters the atmosphere. Dioxygen uptake by Co(salen) occurs in a 2:1 ratio, with two molecules of Co(salen) per one O2.

Figure 2. Structure of Co(Salen).

This was determined from the experiment, because when using 0.615 mmol Co(salen), 3.4 mL of water was displaced. Multiplying this number by the density of atmospheric oxygen showed that about 4.86 mg O2 was displaced, which corresponds to 0.304 mmol O2, nearly an exact half of the Co(salen) used. Previous studies have shown that, depending on the solvent, the cobalt can be four, five or six coordinate and may uptake O2 in either a 1:1 or 2:1 ratio. The solvent DMSO used in this study shows that the cobalt takes coordination of five, with the 5th coordination on one oxygen atom from O2. EXPERIMENTAL 2,2'-[1,2-ethanediylbis(nitrilomethylidyne)]bisphenol. Ethanol (12 mL, 95%) was placed in a test tube with a small magnetic stirring bar and heated to boiling. Salicylaldehyde (1.2 mL, 11.2 mmol) and ehtylenediamine (0.40 mL, 5.6 mmol) were added to the test tube with continued stirring. The solution was stirred for an additional 5 min and cooled in an ice-water bath to precipitate the yellow salen. The precipitate was filtered by vacuum filtration and washed with 2 drops of cold ethanol, allowed to dry, and weighed (1.44 g, 5.4 mmol, 96% yield).

N,N-bis(salicylidene)ethylenediaminocobalt(II). 2,2'-[1,2ethanediylbis(nitrilomethylidyne)]bisphenol (0.96 g, 3.44 mmol) was added to a reaction tube. In a separate reaction tube, cobalt(II) acetate tetrahydrate (0.8 g) was added along with water (3.0 mL) while swirling. Both vessels were flushed with N2 to create an anaerobic atmosphere for ~5 min. Degassed ethanol (24 mL) was added to the reaction tube of salen with and swirled until the yellow crystals dissolved. Next, the cobalt acetate solution was added to the salen and swirled until a brown, gelatinous precipitate formed. The reaction tube was fitted with a balloon filled with N2, and the soln refluxed for ~1 hr with stirring. The reflux was complete when the brown color turned red. Once the change occurred, the soln was cooled to RT, filtered by vacuum filtration and the precipitate washed with ice-cold ethanol (2 mL). The product, Co(salen), was allowed to dry in a dessicator and weighed (1.25 g, 3.84 mmol). To test for dioxygen uptake Co(salen) (200 mg, 0.615 mmol) was placed in a filter flask and covered with a rubber septum. A burette was set upside down and connected to clear hosing, then filled with water (~15 mL). The filter flask was filled with O2 for a couple minutes, and then connected to the hose. The burette was read to note the initial position of the water. DMSO (5 mL) was added dropwise via syringe, causing the Co(salen) to bubble. This made the water level in the burette drop. Once the water level stopped moving the position of the water was read. This was repeated twice. CONCLUSION Co(salen) is a versatile molecule that can take different forms, such as active and inactive. Like proteins in our blood, Co(salen) is capable of reversible dioxygen uptake in either 1:1 or 2:1 ratio, depending on the solvent employed. In DMSO, it is in a 2:1 ratio, with one molecule of Co(salen) attached to each oxygen in O2, forming a sandwich complex of sorts. Co(salen) changes in color when exposed to air as does our blood. The simple structure of Co(salen) allows for studies to easily be done, and serves as a model to study the ways that oxygen carrying proteins work. REFERENCES 1) Atkins, P. Inorganic Chemistry, 4th Edition; W.H. Freeman and Co.: New York, 2006 pp. 219-233