Atomic orbitals, symmetry, and coordination polyhedra

The fundamental ideas on inorganic stereochemistry presented originally by Sidgwick and Powell in 1940 and developed subsequently by Gillespie and Nyh olm in 1957 have expanded into a broad theoretical base for essentially all of coordination chemistry during the subsequent four decades. A key aspect of this work has been a detailed understanding of the topology, shape, and symmetry of all of the actual and plausible polyhedra found in coordinatio n chemistry and the relationship of such properties of the relevant polyhed ra to those of the available atomic orbitals of the central metal atom. Thi s paper reviews the polyhedra for coordination numbers four through nine fo r the spherical nine-orbital sp(3)d(5) manifold commonly used in transition metal coordination chemistry as well as possibilities in coordination comp lexes having other spherical manifolds for the central atom including the f our-orbital sp(3) manifold used by elements without energetically accessibl e d orbitals, the six-orbital sd(5) manifold used in some early transition metal alkyls and hydrides, and the thirteen-orbital sd(5)f(7) manifold used in actinide complexes. (C) 2000 Elsevier Science S.A. All rights reserved.