Jürgen Jacke

Dynamics of metal carbonyls on the infrared time scale : coalescence of CO stretching vibrational bands.

Abstract The variable-temperature IR spectra of (η 4 -norbornadiene)Fe(CO) 3 and related complexes reveal a coalescence phenomenon involving the CO stretching vibrational bands. This is interpreted in terms of fast CO site exchange, rapid enough to equalize the CO force field parameters. A preliminary line shape analysis yields E a ≅ 1.5 kcal mol −1 .

The photochemistry of M(CO)4(η4-norbornadiene) complexes of group 6 transition metals (M = Cr, Mo, W) in low-temperature matrices

Photolysis of M(CO)4(η4-norbornadiene) group 6 metal complexes (1) in low-temperature matrices involves both loss of CO and cleavage of metal—olefin bonds to an extent depending on the metal and on the excitation wavelength. In inert matrices mer-M(CO)3(η4-NBD) (2, M = Cr), fac-M(CO)3(η4-NBD) (3, M = Cr, Mo, W), and trans-vacant M(CO)4(η2-NBD) (7, M = Mo) fragments are observed as primary photoproducts and characterized by means of IR and UV-visible spectroscopy. Secondary wavelength-dependent photoreactions of these fragments include partial regeneration of the starting material and reversible 2 ⇄ 3 photoisomerization (M = Cr). Experiments in 13CO-doped matrices and with 13CO-labelled starting material complement the characterization of 1, 2, and 3 (M = Cr). Remarkably, the cis-vacant M(CO)4(η2-NBD) fragment 9 could not be detected. For all three metals photolysis of 1 in the presence of excess carbon monoxide results in stepwise displacement of the NBD ligand, presumably via the initial formation of 7, yielding M(CO)5(η2-NBD) (4) and M(CO)6. The fragments 2, 3, and 7 can take up N2 from the matrix environment to form mer-M(CO)3(η4-NBD)(N2) (5, M = Cr), fac-M(CO)3(η4-NBD)(N2) (6, M = Cr, Mo, W), and trans-M(CO)4(η2-NBD)(N2) (8, M = Mo) as the major products. The relevance of these results with regard to the mechanism of the photocatalytic hydrogenation of norbornadiene is discussed.