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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.
In the covalent bond classification method, κ 1-carbonate is anX ligand and κ 2-carbonate is an X 2 ligand. With two metals, the number of bonding modes increases because carbonate often serves as a bridging ligand. It can span metal-metal bonds as in [Ru 2 (CO 3) 4 Cl 2] 5-, where again it functions as an (X) 2 ligand.
The greater stabilization that results from metal-to-ligand bonding is caused by the donation of negative charge away from the metal ion, towards the ligands. This allows the metal to accept the σ bonds more easily. The combination of ligand-to-metal σ-bonding and metal-to-ligand π-bonding is a synergic effect, as each enhances the other.
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.
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.
For compounds with doubly bridging CO ligands, denoted μ 2-CO or often just μ-CO, the bond stretching frequency ν CO is usually shifted by 100–200 cm −1 to lower energy compared to the signatures of terminal CO, which are in the region 1800 cm −1. Bands for face-capping (μ 3) CO ligands appear at even lower energies. In addition to ...
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.
Inner sphere electron transfer (IS ET) or bonded electron transfer [1] is a redox chemical reaction that proceeds via a covalent linkage—a strong electronic interaction—between the oxidant and the reductant reactants. In inner sphere electron transfer, a ligand bridges the two metal redox centers during the electron transfer event. Inner ...