IR Spectroscopic Methods for the Investigation of the CO Release from CORMs

Carbon monoxide (CO) is a toxic gas for mammals, and despite this fact, it is naturally produced in these organisms and has been proven to be beneficial in medical treatments, too. Therefore, CO-releasing molecules (CORMs) are intensively developed to administer and dose CO for physiological applications. Nearly all of these compounds are metal carbonyl complexes, which have been synthesized and investigated. However, for most of these CORMs, the exact reaction mechanisms of CO release is not completely elucidated, although it is of utmost importance. The widely used myoglobin assay for testing the CO release has several disadvantages, and therefore, different methods have to be applied to characterize CORMs. In this work, different setups of IR absorption spectroscopy are used to analyze and quantify the CO release during the decay of various CORMs: IR spectroscopy of the gas phase is applied to follow the CO liberation, and attenuated total reflection (ATR) IR spectroscopy is used to record the decay of the metal carbonyl. IR spectroscopy supported by DFT calculations yields valuable insights in the CO release reaction mechanism. The focus is set on two different CORMs: CORM-2 (Ru-2(CO)(6)C-14) and on the photoactive CORM-S1 (photoCORM [Fe(CO)(2)(SCH2CH2NH2)(2)]). Our results indicate that the CO liberation from CORM-2 strongly depends on sodium dithionite, which is required for the commonly applied myoglobin assay and that CORMS] loses all its bound CO molecules upon irradiation with blue light.