Photochemistry of piperidine pentacarbonyl complexes of the Group 6B metals isolated in an argon matrix at 10 K
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Short-wavelength photolysis (λ = 229, 254 nm) of M(CO)5(pip) complexes (pip = piperidine; M = Cr, Mo, W) in Ar matrices at 10 K resulted in the formation of M(CO)4L species with Cs symmetry; long-wavelength photolysis (λ = 366, 405 nm) caused M-L bond breaking and formation of M(CO)5. The structures of the photoproducts were determined by 13CO labeling and force field calculations. The piperidine complexes showed a metal-dependent photochemistry and a reduced photochemical efficiency with respect to other M(CO)5L complexes at all wavelengths. The results are compared with studies of M(CO)5L complexes (M = Cr, W; L = pyridine, pyrazine, NMe3), both in matrices at 10 K and in solutions at room temperature, and are explained by d-orbital energy diagrams derived from photoelectron spectra. © 1980, American Chemical Society. All rights reserved.
author list (cited authors)
Boxhoorn, G., Schoemaker, G. C., Stufkens, D. J., Oskam, A. d., Rest, A. J., & Darensbourg, D. J.