Spin equilibria, transition metal complexes

A change in spin state among transition metal complexes in spin equilibrium invariably involves a change in the electron population of the a antibonding eg orbitals. This produces a substantial change in the properties of the metal-ligand bonds. This variability in the population of a antibonding orbitals is a conspicuous feature of the complexes of the 3d transition metals and accounts for many of their unique properties. 

The results obtained from thermal spin equilibria indicate that AS = 1 transitions are adiabatic. The rates, therefore, depend on the coordination sphere reorganization energy, or the Franck-Condon factors. Radiationless deactivation processes are exothermic. Consequently, they can proceed more rapidly than thermally activated spin-equilibria reactions, that is, in less than nanoseconds in solution at room temperature. Evidence for this includes the observation that few transition metal complexes luminesce under these conditions. Other evidence is the very success of the photoperturbation method for studying thermal spin equilibria intersystem crossing to the ground state of the other spin isomer must be more rapid than the spin equilibrium relaxation in order for the spin equilibrium to be perturbed. 

Nickel(ii) and cobalt(ii) complexes continue to be the most widely studied first-series transition metal complexes. The well resolved NMR spectra arise from the very rapid electron-spin relaxation which occurs as a result of modulation of the zero-field splitting of these ions. In the case of 4-coordinate nickel(ii), only tetrahedral complexes (ground state Ti) are of interest since the square-planar complexes are invariably diamagnetic. Many complexes, however, undergo a square-planar-tetrahedral dynamic equilibrium which can be studied by standard band-shape fitting methods (Section B.l). 

Another simple means of creating ions is a surface ionization source. This works effectively for species having low ionization energies, which in this work include atomic silicon and atomic transition metals. Typically, a rhenium filament resistively heated to about 2200 K is used. Silane or the vapors of a transition metal complex or salt are directed at the filament, where decomposition and ionization occur. It is generally believed that the electronic state distribution of the ions formed is in equilibrium at the filament temperature. This generally produces ground-state ions, e.g., exclusively Si+( P), with a distribution of spin-orbit levels associated with the filament temperature. 

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