Decomposition mechanism of a cobalt-coordinated phosphite–olefin ligand under irradiation

•Coordination behavior of linear and cyclic phosphite–olefin ligands under photolysis conditions.•Arbuzov-like rearrangement of cyclic phosphite–olefin ligand in CpCo(I)-complex.•Suggested mechanism of decomposition of phosphite–olefin ligand.

We herein report on the different coordination behavior of phosphite–olefin ligands containing either a terminal olefin moiety or a related compound containing an internal olefin moiety to a CpCo(I)-center. While the former coordinates to the metal center via P atom and olefin moiety upon irradiation, photolysis of the latter led to the subsequent formation of the phosphorus-free [CpCo(η4-1,3-butadiene)] complex (6). A mechanistic rational of the decomposition reaction based on an Arbuzov-like rearrangement is suggested.

Graphical abstractThe different coordination behaviors of phosphite–olefin ligands possessing terminal and internal olefin moieties to the CpCo(I)-fragment are herein reported. Explicitly the photolysis of ligands with a cyclic olefin moiety yielding the phosphorous-free [CpCo(η4-1,3-butadiene)] complex (6) is discussed and a decomposition mechanism based on an Arbuzov-rearragement is proposed.Figure optionsDownload full-size imageDownload as PowerPoint slide