Several beneficial biological effects of carbon monoxide (CO) have been identified. CO contributes to vascular tone, is anti-inflammatory and antiapoptotic, and protects tissue against hypoxia. In response, a number of novel COreleasing systems, mostly transition-metal carbonyl compounds, have been reported. Recent research in the area of photochemical CO-releasing molecules (PhotoCORMs) is reviewed. The photophysical and chemical properties of these PhotoCORMs are described, along with studies of biological activity in some cases. Spectral data and quantum yields, when available, are compared. In addition, various methods for the detection and quantification of CO are discussed.
Flash and continuous photolysis studies of (μ-pdt)[Fe(CO)(3)](2) under excess CO were conducted in coordinating and noncoordinating solvents. The back-reaction of CO with the photoproduct showed second-order kinetics with k(CO) values of 1.0 × 10(8), 3.4 × 10(6), 1.2 × 10(6), and 0.90 M(-1) s(-1) in hexanes, benzene, toluene, and THF, respectively. These data indicate a solvent-coordinated intermediate as one photoproduct, but other long-lived species were also apparent.
Time-resolved infrared spectroscopic studies have been used to characterize the reactive intermediate CH3C(O)Co(CO)2PPh3 (ICo), which is relevant to the mechanism of the catalysis of alkene hydroformylation by the phosphine-modified cobalt carbonyls. Step-scan FTIR and (variable) single-frequency time-resolved infrared detection on the microsecond time scale were used to record the spectrum of ICo and to demonstrate that the principal photoproduct of the subsequent reaction of this species at PCO = 1 atm is the methyl cobalt complex CH3Co(CO)3PPh3 (MCo). At higher PCO the trapping of ICo with CO to re-form CH3C(O)Co(CO)3PPh3 (ACo) (rate = kCO[CO][ICo]) was shown to become competitive with the rate of acetyl-to-cobalt methyl migration to give MCo (rate = kM[ICo]). Activation parameters for the competing pathways in benzene were determined to be delta H++CO = 57 +/- 04 kJ mol-1, delta S++CO = -91 +/- 12 J mol-1 K-1 and delta H++M = 40 +/- 2 kJ mol-1, delta S++M = -19 +/- 5 J mol-1 K-1. The effects of varying the solvent on the competitive reactions of ICo were also explored, and the mechanistic implications of these results are discussed.
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