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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.
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.
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.
It is a common acetylacetonate complex of titanium. It is a red-orange solid that hydrolyzes slowly in air. [1] The complex is prepared by treatment of titanium tetrachloride with excess acetylacetone: [1] TiCl 4 + 2 Hacac → Ti(acac) 2 Cl 2 + 2 HCl. It is an octahedral complex that crystallizes as a racemic mixture of the chiral cis isomers. [2]
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.
Cisplatin, PtCl 2 (NH 3) 2, is a coordination complex of platinum(II) with two chloride and two ammonia ligands.It is one of the most successful anticancer drugs. A coordination complex is a chemical compound consisting of a central atom or ion, which is usually metallic and is called the coordination centre, and a surrounding array of bound molecules or ions, that are in turn known as ligands ...
[9] One of these compounds, the cis-bis(ethylenediamine)dinitrocobalt(III) bromide, was the first synthesis of a chiral octahedral cobalt complex. In 1991, the Swiss Committee on Chemistry donated Humphrey's chiral crystals to the Royal Society of Chemistry, and they are now at Burlington House, in London. [10]
The rate of reductive elimination is greatly influenced by the geometry of the metal complex. In octahedral complexes, reductive elimination can be very slow from the coordinatively saturated center; and often, reductive elimination only proceeds via a dissociative mechanism, where a ligand must initially dissociate to make a five-coordinate ...
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