PHOTOCHEMISTRY OF PIPERIDINE PENTACARBONYL COMPLEXES OF THE GROUP-6B METALS ISOLATED IN AN ARGON MATRIX AT 10 K uri icon

abstract

  • Short-wavelength photolysis ( = 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 ( = 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.

published proceedings

  • INORGANIC CHEMISTRY

author list (cited authors)

  • BOXHOORN, G., SCHOEMAKER, G. C., STUFKENS, D. J., OSKAM, A., REST, A. J., & DARENSBOURG, D. J.

citation count

  • 14

complete list of authors

  • BOXHOORN, G||SCHOEMAKER, GC||STUFKENS, DJ||OSKAM, A||REST, AJ||DARENSBOURG, DJ

publication date

  • November 1980