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The energies of transitions correlate with the order of the electrochemical series. The metal ions that are most easily reduced correspond to the lowest energy transitions. The above trend is consistent with transfer of electrons from the ligand to the metal, thus resulting in a reduction of metal ions by the ligand.
Carbon monoxide-releasing molecules are metal carbonyl complexes that are being developed as potential drugs to release CO. At low concentrations, CO functions as a vasodilatory and an anti-inflammatory agent. CO-RMs have been conceived as a pharmacological strategic approach to carry and deliver controlled amounts of CO to tissues and organs. [63]
A spectrochemical series is a list of ligands ordered by ligand "strength", and a list of metal ions based on oxidation number, group and element.For a metal ion, the ligands modify the difference in energy Δ between the d orbitals, called the ligand-field splitting parameter in ligand field theory, or the crystal-field splitting parameter in crystal field theory.
CO is a well-known strong pi-accepting ligand in organometallic chemistry that will labilize in the cis position when adjacent to ligands due to steric and electronic effects. The system most often studied for the cis effect is an octahedral complex M(CO) 5 X where X is the ligand that will labilize a CO ligand cis to it.
Thus the reorganization energy for chemical redox reactions, which is a Gibbs free energy, is also a parabolic function of Δe of this hypothetical transfer, For the self exchange reaction, where for symmetry reasons Δe = 0.5, the Gibbs free energy of activation is ΔG(0) ‡ = λ o /4 (see Fig. 1 and Fig. 2 intersection of the parabolas I and ...
In cases where the ligand has low energy LUMO, such orbitals also participate in the bonding. The metal–ligand bond can be further stabilised by a formal donation of electron density back to the ligand in a process known as back-bonding. In this case a filled, central-atom-based orbital donates density into the LUMO of the (coordinated) ligand.
Considering both weak and strong ligand fields, a Tanabe–Sugano diagram shows the energy splitting of the spectral terms with the increase of the ligand field strength. It is possible for us to understand how the energy of the different configuration states is distributed at certain ligand strengths.
σ bonding from electrons in CO's HOMO to metal center d-orbital. π backbonding from electrons in metal center d-orbital to CO's LUMO. The electrons are partially transferred from a d-orbital of the metal to anti-bonding molecular orbitals of CO (and its analogs). This electron-transfer strengthens the metal–C bond and weakens the C–O bond.