Photolysis of hexacarbonyltungsten(0) in the presence of acryloylferrocene in n-hexane solution at 10 C yields pentacarbonyl(eta(2)-acryloylferrocene)tungsten(0) (1) as the only photo-substitution product, different from the general reaction pattern observed for the Group 6 metal carbonyls with other olefins. W(CO)5(eta(2)-acryloylferrocene) (1) decomposes in solution to the parent hexacarbonyltungsten(0) and free acryloylferrocene. Trimethylphosphite was introduced as ligand into the molecule to increase the stability. The photolysis of pentacarbonyl(trimethylphosphite)tungsten(0) in the presence of acryloylferrocene in n-hexane solution at 10 degrees C yields only Cis-W(CO)(4)[P(OCH3)(3)](eta(2)-acryloylferrocene) (2) as the monosubstitution product. Both eta(2)-acryloylferrocene complexes (1 and 2) could be isolated and characterized by MS, IR and NMR spectroscopy. The trimethylphosphite complex (2) is found to be even less stable than W(CO)(5)( eta(2)-acryloylferrocene) (1). (c) 2006 Elsevier B.V. All rights reserved.