1,6-Methano[10]annulene as prospective organometallic ligand from the annulene family A DFT study of transition metal π-complexes and their inter-ring haptotropic rearrangements

I.P. Gloriozov (1) , N.S. Zhulyaev (1) , F. Gam (2) , J.-Y. Saillard (2) , Y.F. Oprunenko (1)

1 MSU - Lomonosov Moscow State University
2 ISCR - Institut des Sciences Chimiques de Rennes

The structural peculiarities (C1-C6 distances, bending of the ligand, conformation of organometallic group relative to the ligand, etc.), the isomerism and the mechanisms of inter-ring haptotropic rearrangements (IRHR) in Cr(CO)3 and CoCp complexes of 1,6-methano[10]annulene were investigated by DFT. An activation barrier of 28.0 kcal/mol, lower than that corresponding to naphthalene, was computed for the η6, η6-IRHR in the mononuclear chromium complex. In the case of the mononuclear cobalt species, activations barrier of 33.8 and 31.3 kcal/mol were computed for the η4, η4-IRHR in the trans and cis isomers, respectively.

Keywords: Annulenes; DFT; Inter-ring haptotropic rearrangements IRHR; Polyaromatic hydrocarbons; Transition metal complexes

Domains: Chemical Sciences; Coordination chemistry

I.P. Gloriozov, N.S. Zhulyaev, F. Gam, J.-Y. Saillard, Y.F. Oprunenko. 1,6-Methano[10]annulene as prospective organometallic ligand from the annulene family A DFT study of transition metal π-complexes and their inter-ring haptotropic rearrangements. Journal of Organometallic Chemistry, 2018, 867, pp.306-311. ⟨10.1016/j.jorganchem.2017.11.023⟩. ⟨hal-01809148⟩