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In inorganic chemistry, the cis effect is defined as the labilization (or destabilization) of CO ligands that are cis to other ligands. 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.
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.
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.
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 ...
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.
Mechanism proposed for Kumada coupling (L = Ligand, Ar = Aryl). In such cases, the mechanism generally involves reductive elimination of R-R' from L n MR(R') (L = spectator ligand). This intermediate L n MR(R') is formed in a two-step process from a low valence precursor L n M. The oxidative addition of an organic halide (RX) to L n M gives L n ...
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.
The structural trans effect can be measured experimentally using X-ray crystallography, and is observed as a stretching of the bonds between the metal and the ligand trans to a trans-influencing ligand. Stretching by as much as 0.2 Å occurs with strong trans-influencing ligands such as hydride.