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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. Unlike the trans effect, which is most often observed in 4-coordinate square planar complexes, the cis effect is observed in 6-coordinate octahedral transition metal complexes.
Very often, cis–trans stereoisomers contain double bonds or ring structures. In both cases the rotation of bonds is restricted or prevented. [4] When the substituent groups are oriented in the same direction, the diastereomer is referred to as cis, whereas when the substituents are oriented in opposing directions, the diastereomer is referred to as trans.
In an octahedral complex, this degeneracy is lifted. The energy of the d z 2 and d x 2 − y 2 , the so-called e g set, which are aimed directly at the ligands are destabilized. On the other hand, the energy of the d xz , d xy , and d yz orbitals, the so-called t 2g set, are stabilized.
In an octahedral complex, the molecular orbitals created by coordination can be seen as resulting from the donation of two electrons by each of six σ-donor ligands to the d-orbitals on the metal. In octahedral complexes, ligands approach along the x -, y - and z -axes, so their σ-symmetry orbitals form bonding and anti-bonding combinations ...
The ligand can bend so that one donor atom is at the pole and the remaining three are on the equator of the central atom. This is called cis-β (beta). The remaining octahedral positions are cis (adjacent) to each other. The triangles of coordinating atoms and the central atom have two coplanar atoms, and one perpendicular atom.
In inorganic chemistry, the trans effect is the increased lability of ligands that are trans to certain other ligands, which can thus be regarded as trans-directing ligands. It is attributed to electronic effects and it is most notable in square planar complexes , although it can also be observed for octahedral complexes. [ 1 ]
The descriptors cis (Latin, on this side of) [2] and trans (Latin, over, beyond) [3] are used in various contexts for the description of chemical configurations: [4] [5] In organic structural chemistry , the configuration of a double bond can be described with cis and trans , in case it has a simple substitution pattern with only two residues.
(Similar procedures can give cis,trans isomers of 1,4-cyclooctadiene and 1,5-cyclooctadiene). [2] In addition, a photochemical method exists for the direct cis–trans isomerisation. Although this equilibrium strongly favours the more stable cis form, the reaction can be driven towards the trans form by trapping with silver ions. [11] [12]