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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 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. The position of two residues relative to one another at different points in a ring system or a larger molecule can also be described with cis and trans if the structure's ...
The insertion of carbon monoxide into a metal-carbon bond to form an acyl group is the basis of carbonylation reactions, which provides many commercially useful products. Mechanistic studies reveal that the alkyl group migrates intramolecularly to an adjacent CO ligand. [2] [3] CO Insertion reaction pathway for an octahedral complex
One classic example of the trans effect is the synthesis of cisplatin and its trans isomer. [5] The complex PtCl 4 2− reacts with ammonia to give [PtCl 3 NH 3] −. A second substitution by ammonia gives cis-[PtCl 2 (NH 3) 2], showing that Cl- has a greater trans effect than NH 3. The procedure is however complicated by the production of ...
The term "octahedral" is used somewhat loosely by chemists, focusing on the geometry of the bonds to the central atom and not considering differences among the ligands themselves. For example, [Co(NH 3) 6] 3+, which is not octahedral in the mathematical sense due to the orientation of the N−H bonds, is referred to as octahedral. [2]
In the example shown below, the para-methoxybenzoyl substituent serves primarily as a source of steric bulk to allow the catalyst to differentiate the two faces of the alkene. [23] SAD scheme 3. It is often difficult to obtain high diastereoselectivity on cis-disubstituted alkenes when both ends of the olefin have similar steric environments.
Molybdenum hexacarbonyl is a popular reagent in academic research. [6]One or more CO ligands can be displaced by other ligands. [7] Mo(CO) 6, [Mo(CO) 3 (MeCN) 3], and related derivatives are employed as catalysts in organic synthesis for example, alkyne metathesis and the Pauson–Khand reaction.
trans-Cyclooctene was first synthesized on a preparatory scale by Arthur C. Cope with a Hofmann elimination reaction of N,N,N-trimethylcyclooctylammonium iodide. [10] The reaction gives a mixture of cis and trans isomers, and the trans isomer is selectively trapped as a complex with silver nitrate.