ELECTRONIC AND LIGAND STRUCTURE DICTATED EFFECTS FOR TRIGONAL, TETRAGONAL AND RHOMBIC SYMMETRIES OF TRANSITION METAL CAGE COMPLEXES

Abstract

Spectroscopic and structural data of series of complexes with widely varied metal centers (d⁰ to d¹⁰) and an identical ligand sphere (figure) are presented. The structures comprise a range from near octahedral to near trigonal prismatic geometries and also involving additional small tetragonal perturbations. The complete series allows for an analysis of the various influences, viz. bonding and non-bonded interactions which dictate the compromise structure. Axial and rhombic distortions in solution and solid state of selected examples are discussed on the basis of electronic and EPR spectroscopy and trigonal distortions are analyzed on the basis of twist angles calculated from X-ray data.