Synthesis, Structural Characterization and Photodecarbonylation Study of a Dicarbonyl Ruthenium(II)-Bisquinoline Complex.

A photoactivatable ruthenium(II) carbonyl complex mer,cis-[Ru(II)Cl(BisQ)(CO)2]PF6 2 was prepared using a tridentate bisquinoline ligand (BisQ=(2,6-diquinolin-2-yl)pyridin). Compound 2 was thoroughly characterized by standard analytical methods and single crystal X-ray diffraction. The crystal structure of the complex cation reveals a distorted octahedral geometry. The decarbonylation upon exposure to 350 and 420 nm light was monitored by UV/VIS absorbance and Fourier transform infrared spectroscopies in acetonitrile and 1 % (v/v) DMSO in water, respectively. The kinetic of the photodecarbonylation has been elucidated by multivariate curve resolution alternating least-squares analysis. The stepwise decarbonylation follows a serial mechanism. The first decarbonylation occurs very quickly whereas the second decarbonylation step proceeds more slowly. Moreover, the second rate constant is lower in 1 % (v/v) DMSO in water than in acetonitrile. In comparison to 350 nm irradiation, exposure to 420 nm light in acetonitrile results in a lower second rate constant.