Cyclopentadienyl and indenyl molybdenum(II) complexes bearing planar N,N,N-chelating ligands

The reactivity of cyclopentadienyl and indenyl molybdenum(II) complexes [(eta(5)-Cp')Mo(CO)(2)(NCMe)(2)] [BF4] (Cp' = Cp, Ind, 1,3-Ph2C9H5) with a series of planar N,N,N-chelating ligands was scrutinized. The planar N,N,N-chelating ligands give kappa(2)-complexes [(eta(5)-Cp')Mo(Co)(2)(kappa(2)-L-N'N'N][BF4] those undergo in particular cases a spontaneous release of carbon monoxide to give [(eta(5)-Cp')Mo(Co)(kappa(3)-L-N,L-N,L-N)][BF4], depending on several factors including the basicity of the tridentate ligand as well as the nature of the starting molybdenum(II) compound. This behaviour strongly contrasts with tripodal ligands those do not affect cis-Mo(CO)(2) moiety even upon tridentate coordination. All structure types, discussed in this work, were elucidated by the spectroscopic measurements as well as by the X-ray crystallography. (C) 2014 Elsevier B.V. All rights reserved.