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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.
For ML a 4 L b 2, two isomers exist.These isomers of ML a 4 L b 2 are cis, if the L b ligands are mutually adjacent, and trans, if the L b groups are situated 180° to each other. It was the analysis of such complexes that led Alfred Werner to the 1913 Nobel Prize–winning postulation of octahedral complexes.
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.
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 ...
For example, in the rock salt ionic structure each sodium atom has six near neighbour chloride ions in an octahedral geometry and each chloride has similarly six near neighbour sodium ions in an octahedral geometry. In metals with the body centred cubic (bcc) structure each atom has eight nearest neighbours in a cubic geometry.
Structure of an octahedral metal aquo complex. Chromium(II) ion in aqueous solution. Most aquo complexes are mono-nuclear, with the general formula [M(H 2 O) 6] n+, with n = 2 or 3; they have an octahedral structure. The water molecules function as Lewis bases, donating a pair of electrons to the metal ion and forming a dative covalent bond ...
A related class of octahedral clusters are of the type M 6 X 8 L 6 where M is a metal usually of group 6 or group 7, X is a ligand and more specifically an inner ligand of the chalcohalide group such as chloride or sulfide and L is an "outer ligand." The metal atoms define the vertices of an octahedron.
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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