d Orbitals in Compounds of Second-Row Elements. II. Comparison of H, C, F, and Cl as Ligands

Abstract

Calculations have been made to contrast the effects of H, C, F, and Cl as ligands on loosely bound d orbitals of second‐row elements. Sets of one, two (at right angles), four (square), and six (octahedral) identical atoms are compared. The approximation is electrostatic, with the use of potentials derived from self‐consistent field wave functions. The order of effectiveness is F>Cl>C≫H. The first three are more nearly equal in their perturbing power than expected from their electronegativities, and hydrogen is surprisingly ineffective. The conclusions lend themselves to some generalization to the conditions of binding in second‐row elements. These are discussed, and some examples given.