Palladium(II) and Platinum(II) Bis(Stibinidene) Complexes with Intramolecular Hydrogen-Bond Enforced Geometries

The coordination capability of two N,C,N pincer coordinated stibinidenes, i. e. bis(imino)- [2,6-(DippN=CH)2C6H3]Sb (1) or imino-amino- [2-(DippN=CH)-6-(DippNHCH2)C6H3]Sb (2) toward palladium(II) and platinum(II) centers was examined. In the course of this study, seven new square-planar bis(stibinidene) complexes were synthesized and characterized by NMR, IR, Raman, UV-vis spectroscopy and single crystal (sc)-X-ray diffraction analysis. In all cases, both stibinidene ligands 1 or 2 adopt trans positions, but differ significantly in the torsion angle describing mutual orientation of aromatic rings of the stibinidenes along the Sb-Pd/Pt-Sb axes. Furthermore, majority of complexes form isomers in solution most probably due to a hindered rotation around Sb-Pd/Pt bonds caused by bulkiness of 1 and 2. This phenomenon also seems to be influenced by the absence/presence of a pendant -CH2NH- group in 1/2 that is able to form intramolecular hydrogen bonds with the adjacent chlorine atom(s) attached to the metal centers. The whole problem was subjected to a theoretical study focusing on the role of hydrogen bonds in structure architecture of the complexes. To describe the UV-vis spectra of these highly coloured complexes, TD-DFT calculations were employed. These outline differences between the stibinidene ligands, the transition metals as well as between the charge of the complexes (neutral or anionic). The coordination capability of two N,C,N pincer chelated stibinidenes (1 and 2) toward palladium(II) and platinum(II) centres is reported. This study reveals significant structural differences between these ligands caused mainly by the formation of hydrogen bonds via pendant NH groups of 2.image