Metal-ligand bonds, strength

Hertwig, R.H., Hrusak, J., Schroder, D., Koch, W. and Schwarz, H. (1995) The metal-ligand bond strengths in cationic gold(l) complexes. Application of approximate density functional theory. Chemical Physics Letters, 236, 194-200. 

In the chemistry of main-group element sulfoxide complexes, a relationship between Aj/(S=0) and the enthalpy of formation of the sulfoxide complex has been derived (159). The applicability of the equation has only been examined for O-l SO complexes, and the constraints on using Ai (S=0) as a measure of metal-ligand bond strength should be borne in mind during its application. 

A. R. Dias, J. A. Martinho Simoes. On the Evaluation of Metal-Ligand Bond Strengths in Mf-CfllOifl Complexes. Rev. Port. Quim. 1982, 24, 191-199. 

Vibrational frequencies measured in IR experiments can be used as a probe of the metal—ligand bond strength and hence for the variation of the electronic structure due to metal—radical interactions. Theoretical estimations of the frequencies are obtained from the molecular Hessian, which can be straightforwardly calculated after a successful geometry optimization. Pure density functionals usually give accurate vibrational frequencies due to an error cancellation resulting from the neglect of... 

A third limitation arises because metal-ligand bond strengths in compounds formed by the transition metal elements located toward the bottom of the periodic table are generally greater than the bond strengths of the corresponding species that contain elements found... 

Metal ligand bond strengths via analysis of vibrational frequencies. 

The rate of reaction correlates with the metal-ligand bond strength of the leaving group, in a hnear free energy relationship (LFER, explained in the next section). 

Berezin has also used the kinetics of hydrolysis as a guide to metal-ligand bond strength 19). The order of stability found was Fe(III) > Ag >Mg > Pb > Cd, Hg > Ca. However, kinetic slowness may be due to a high activation energy rather than a low bond energy. 

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